CN109563186A - The manufacturing method of modified conjugated diene polymer and the manufacturing method of polymer composition - Google Patents

The manufacturing method of modified conjugated diene polymer and the manufacturing method of polymer composition Download PDF

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CN109563186A
CN109563186A CN201780047567.6A CN201780047567A CN109563186A CN 109563186 A CN109563186 A CN 109563186A CN 201780047567 A CN201780047567 A CN 201780047567A CN 109563186 A CN109563186 A CN 109563186A
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polymer
compound
alkyl
conjugated diene
formula
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CN109563186B (en
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青嶋纮
今井昌子
稻垣胜成
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/26—Incorporating metal atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/25—Incorporating silicon atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
    • C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
    • C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers

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Abstract

The present invention relates to the manufacturing method of modified conjugated diene polymer, the step of unit based on aforementioned modifiers in the conjugated diene polymer of the unit made with based on the monomer for including conjugated diene compound and the unit based on the modifying agent with silicon atom, tin atom, germanium atom or phosphorus atoms is reacted with organo-metallic compound is included.

Description

The manufacturing method of modified conjugated diene polymer and the manufacture of polymer composition Method
Technical field
The present invention relates to the manufacturing method of modified conjugated diene polymer and contain the polymer composition of the polymer Manufacturing method.
Background technique
In recent years, since the concern to environmental problem improves, the requirement to province's burnup of automobile enhances, to automobile The polymer composition used in tire also requires province's burnup excellent.As the polymer composition of automobile tire, make With containing the fillers such as polybutadiene, butadiene-styrene copolymer equiconjugate diene polymer and carbon black, silica Polymer composition etc..For example, proposing as the good polymer composition of burnup is saved containing gathering conjugated diene Close object use with dialkyl amido it is alkoxysilane-modified obtained from polymer polymer composition, the conjugated diene Based polymer be using lithium alkylide as polymerization initiator by polymerizing butadiene or by butadiene and it is styrene copolymerized obtained from (referring to patent document 1,2).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 63-186748 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2005-290355 bulletin.
Summary of the invention
Problems to be solved by the invention
Sometimes viscosity rises such good polymer composition of province's burnup at any time.Therefore, to using conjugated diene The polymer composition of polymer it is also desirable to have storage stability while requiring province's burnup good.Based on the feelings Condition, the invention solves project be to provide that can to obtain province's burnup functional and poly- with excellent storage stability The manufacturing method of the modified conjugated diene polymer of polymer composition.
The means used to solve the problem
The present invention relates to the manufacturing method of modified conjugated diene polymer, include make conjugated diene polymer with it is organic The step of metallic compound is had an effect, the conjugated diene polymer have based on the monomer comprising conjugated diene compound Unit and unit based on the modifying agent with silicon atom, tin atom, germanium atom or phosphorus atoms.
The invention further relates to the manufacturing method of polymer composition, include total to the modification made by the above method 100 mass parts of yoke diene interpolymer are kneaded the step of supporting material of 10 ~ 150 mass parts.
Invention effect
By the invention it is possible to provide can obtain province's burnup it is functional and with excellent storage stability polymer The manufacturing method of the modified conjugated diene polymer of composition.
Specific embodiment
For present embodiment, it is described in detail.It should be noted that the present invention is not limited to the following embodiments and the accompanying drawings.
In this specification, alkyl is indicated from eliminating 1 valence group obtained from 1 hydrogen atom in hydrocarbon.Alkylene indicate from Divalent group obtained from 2 hydrogen atoms is eliminated in hydrocarbon.Oxyl indicates that there is the hydrogen atom of hydroxyl to be obtained by alkyl substitution Structure 1 valence group.Amino (being also denoted as the amino replaced sometimes below) with substituent group indicates there is at least the 1 of amino A hydrogen atom by other than hydrogen atom 1 valence atom or 1 valence group replacement obtained from structure group or with amino The group of structure obtained from 2 hydrogen atoms are substituted by divalent group.Alkyl with substituent group (is also denoted as replacing below sometimes Alkyl) indicate have alkyl at least one hydrogen atom be substituted base substitution obtained from structure 1 valence group.With nitrogen original The alkylene of son and/or oxygen atom refers to the carbon atom in alkylene other than the carbon atom for being removed hydrogen atom And/or the divalent group of hydrogen atom structure obtained from the group substitution with nitrogen-atoms and/or oxygen atom.
[manufacturing method of modified conjugated diene polymer]
The manufacturing method of the modified conjugated diene polymer of present embodiment, which includes, makes conjugated diene polymer and organic gold Belong to the step of compound is had an effect, the conjugated diene polymer has based on the monomer comprising conjugated diene compound Unit and unit based on the modifying agent with silicon atom, tin atom, germanium atom or phosphorus atoms.The step can be make it is aforementioned The step of unit based on aforementioned modifiers of conjugated diene polymer is reacted with organo-metallic compound.
Conjugated diene polymer involved in present embodiment can have in the end of the polymer is based on modifying agent Unit, can also have the unit based on modifying agent in the strand of the polymer, can also be in the end of the polymer With in strand have the unit based on modifying agent.In general, there are burnup performances if the functional group number of modifying agent is more Excellent tendency, there are the tendencies of poor storage stability.
In the case where the end of polymer has the unit based on modifying agent, modified conjugation involved in present embodiment Diene polymer can be made by the following method.
Firstly, making the monomer polymerization comprising conjugated diene compound in the presence of polymerization initiator as step 1, obtaining To the polymer of active end.Then, as step 2, make with the official that can be reacted with the reactive terminal of the polymer The aforementioned modifiers that can be rolled into a ball and the polymer reaction import the unit based on aforementioned modifiers in the end of the polymer.At this point, It can be generated and coexist the polymer of dimer obtained from the polymer connection via modifying agent by 2 or more or more.And And as step 3, organo-metallic compound is added to the polymer with the unit based on aforementioned modifiers, is made based on aforementioned The unit of modifying agent is reacted with organo-metallic compound, thus obtains the polymerization of modified conjugated diene involved in present embodiment Object.
In the case where importing unit based on modifying agent in the strand of polymer, it can be used that have can be with conjugation The aforementioned modifiers of the functional group of diolefin compound copolymerization.For example, as step 1', make in the presence of polymerization initiator include When the monomer polymerization of conjugated diene compound, changed by making with the aforementioned of functional group that can be copolymerized with conjugated diene compound Property agent polymerize together, thus obtain in the strand of polymer with the unit based on aforementioned modifiers polymer.Then, As step 3', organo-metallic compound is added to the polymer with the unit based on aforementioned modifiers, makes to change based on aforementioned Property agent unit reacted with organo-metallic compound, thus obtain modified conjugated diene involved in present embodiment polymerization Object.At this point, making aforementioned modifiers and step with the functional group that can be reacted with the reactive terminal of polymer as step 2' Polymer reaction obtained in 1' imports the unit based on aforementioned modifiers in the end of the polymer, and thus, it is possible to obtain Conjugated diene polymer in the end of the polymer and strand with the unit based on modifying agent passes through progress thereafter Abovementioned steps 3' can obtain corresponding modified conjugated diene polymer.
In addition, can be used can be together in the case where importing the unit based on modifying agent in the strand of polymer The conjugated diene compound and/or aromatic vinyl compound of conjugate diene compound copolymerization, have that can be converted into can be with The functional group at the position of modifying agent reaction.For example, making in the presence of polymerization initiator as step 1'' comprising conjugated diene When the monomer polymerization of compound, allow to be copolymerized and have with conjugated diene compound to be converted into and can react with modifying agent Position functional group conjugated diene compound and/or aromatic vinyl compound (such as 4- methyl styrene) polymerize together And after obtaining polymer, carrying out conversion of the functional group to the position that can be reacted with modifying agent (such as makes to have based on 4- first The polymer of the unit of base styrene and organo-metallic compound have an effect and slough hydrogen from methyl), making to have can be with The aforementioned modifiers of the functional group of functional group reactions after the conversion react with it, and thus, it is possible to obtain point in polymer With the polymer of the unit based on aforementioned modifiers in subchain.Then, as step 3'', aforementioned modifiers are based on to having Unit polymer add organo-metallic compound, react the unit based on aforementioned modifiers with organo-metallic compound, Thus modified conjugated diene polymer involved in present embodiment is obtained.At this point, as step 2'', making to have can be with Polymer reaction obtained in the aforementioned modifiers and step 1'' of the functional group of the reactive terminal reaction of polymer, in the polymerization The end of object imports the unit based on aforementioned modifiers, and thus, it is possible to obtain having base in the end of the polymer and strand In the conjugated diene polymer of the unit of modifying agent, thereafter, by carrying out abovementioned steps 3'', corresponding modification can be obtained Conjugated diene polymer.
Hereinafter, for be able to use in the manufacture of modified conjugated diene polymer involved in present embodiment it is each at Divide and is illustrated.
(monomer)
As conjugated diene compound, it can be cited for example that 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3- dimethyl- 1,3-butadiene and 1,3- hexadiene, preferably 1,3-butadiene or isoprene.
Monomer involved in present embodiment can include aromatic vinyl while comprising conjugated diene compound Close object.As aromatic vinyl compound, it can be cited for example that styrene, α-methylstyrene, vinyltoluene, vinyl Naphthalene, divinylbenzene, trivinylbenzene and divinyl naphthalene, preferably styrene.
The content of aromatic vinyl compound in monomer using the total amount of monomer as 100 mass %, preferably 5 mass % with Upper, more preferably 14 mass % or more.In addition, the content of aromatic vinyl compound is in order to improve province's burnup, preferably 50 matter Measure % or less, more preferably 45 mass % or less.
(vinyl agent)
The production of above-mentioned conjugated diene polymer can adjust the vinyl for being originated from the monomeric unit of conjugated diene compound The reagent of bonded amount, is originated from aromatics at the monomeric unit from conjugated diene compound in adjusting conjugated diene polymer chain Reagent (the following general name note of the distribution of the monomeric unit of vinyl compound and the monomeric unit from compound in addition to this Make " regulator ") in the presence of carry out.
As regulator, ether compound, tertiary amine, phosphine compound, alkali metal alkanolates, alkali metal phenolate etc. can be enumerated. As ether compound, it can be cited for example that tetrahydrofuran, oxinane, the isothrausmatic ether of Isosorbide-5-Nitrae-dioxane；Diethyl The aliphatic monoethers such as ether, dibutyl ethers；The aliphatic such as ethylene glycol dimethyl ether, ethylene glycol Anaesthetie Ether, ethylene glycol dibutyl ethers Diether；Three ether of the aliphatic such as diethylene glycol diethyl ether, diethylene glycol dibutyl ether；Diphenyl ether, methyl phenyl ethers anisole, 1,2- dimethoxy The aromatic oxides such as base benzene, 3,4- dimethoxy-p.As tertiary amine, it can be cited for example that triethylamine, tripropylamine, tributyl Amine, 1,1,2,2- tetramethylethylenediamine, N, N- diethylaniline, pyridine and quinoline.As phosphine compound, it can be cited for example that three Methylphosphine, triethyl phosphine and triphenylphosphine.As alkali metal alkanolates, it can be cited for example that sodium tert-butoxide, potassium tert-butoxide, uncle penta Sodium alkoxide and tert-pentyl alcohol potassium.As alkali metal phenolate, it can be cited for example that sodium phenate and potassium phenate.They can be applied in combination 2 kinds More than.
(polymerization initiator)
As polymerization initiator, the complex compound of alkali metal, alkali metal and polar compound can be enumerated, with the oligomeric of alkali metal Object, organic alkali metal compound, ziegler natta catalyst, ferrocene catalyst, the conjugated diene of active end are poly- Close object etc..As polymerization initiator, preferably organic alkali metal compound.These polymerization initiators can be applied in combination 2 kinds with On.
As alkali metal, it can be cited for example that lithium, sodium, potassium, rubidium and caesium.Complexing as alkali metal and polar compound Object, it can be cited for example that potassium-tetrahydrofuran complex and potassium-diethoxyethane complex compound.As with the oligomeric of alkali metal Object, it can be cited for example that the sodium salt etc. of the α-methylstyrene tetramer.As organic alkali metal compound, it can be cited for example that tool There are the organic alkali metal compound of the group of nitrogen atom and the organic alkali metal compound with alkyl.
As the organic alkali metal compound with alkyl, it can be cited for example that ethyl-lithium, n-propyl lithium, isopropyl lithium, N-BuLi, s-butyl lithium, t-octyl lithium, positive decyl lithium, phenyl lithium, 2- naphthalene lithium, 2- butyl phenyl lithium, 4- phenyl butyl Lithium, cyclohexyl lithium, cyclopenta lithium, bis- lithium of 1,4- are for butane, bis- lithium of 1,4- generation -2- butylene, tri- lithium of 1,3,5- for benzene, 1,3,5- tri- (lithium Dai Jiaji) benzene, 2,3,5- tri- (lithium Dai Jiaji) naphthalenes, Isosorbide-5-Nitrae, 5- tri- (lithium Dai Jiaji) naphthalene, naphthalene sodium, biphenyl sodium and naphthalene potassium, preferably For n-BuLi.
It is preferably following that there is base shown in formula (2) as the organic alkali metal compound of the group with nitrogen atom The organic alkali metal compound of group.
[changing 1]
。
In formula (2), R21And R22Alkyl or trihydrocarbylsilyl groups optionally with substituent group is each independently represented, or Person optionally forms R21In a part and R22In a part bonding obtained from optionally with nitrogen-atoms and/or oxygen atom Alkylene ,-Si (R32)2-(CH2)x-Si(R32)2Shown in carbon atom number be 5 or more and 20 group (R below32Indicate hydrocarbon Base, x are 1 or more and 10 integers below) or-Si (R33)2-(CH2)yShown in carbon atom number be 4 or more and 20 below Group (R33Indicate that alkyl, y are 2 or more and 11 integers below).
As R21And R22In alkyl, it can be cited for example that alkyl, alkenyl, alkynyl, aryl and aralkyl.As alkyl, It can be cited for example that methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, just pungent Base, dodecyl, cyclopenta and cyclohexyl.As alkenyl, it can be cited for example that vinyl, allyl, 1- acrylic and different Acrylic.As alkynyl, it can be cited for example that acetenyl and 2-propynyl.As aryl, it can be cited for example that phenyl, methylbenzene Base, ethylphenyl, benzyl, tolyl and xylyl.As aralkyl, it can be cited for example that benzyl.It is excellent as alkyl It is selected as alkyl, more preferably carbon atom number is 1 or more and 4 alkyl below.
As R21And R22In the alkyl with substituent group, it can be cited for example that 1 or more the substituted ammonia of hydrogen atom Alkyl obtained from alkyl obtained from base substitution, 1 or more hydrogen atom are substituted by oxyl, 1 or more hydrogen atom quilt Obtained from alkyl obtained from trialkylsilkl substitution, 1 or more hydrogen atom are substituted by trialkoxysilyl Alkyl etc..
Here, as substituted amino, it can be cited for example that N, N- dimethylamino, N, the N, N- such as N- diethylamino bis- The cyclic aminos such as alkyl amino, 1- pyrrole radicals, 1- piperidyl, 1- imidazole radicals.
As alkyl obtained from the substituted amino substitution of 1 or more hydrogen atom, it can be cited for example that N, N- diformazan Base amino methyl, 2- (N, N- dimethylamino) ethyl, 2- (N, N- diethylamino) ethyl, 3- (N, N- dimethylamino) third (N, the N- dialkyl amido) alkyl such as base, 3- (N, N- diethylamino) propyl；4- (N, N- dimethylamino) phenyl, 3- (N, N- dimethylamino) (N, the N- dialkyl group such as phenyl, 4- (N, N- diethylamino) phenyl, 3- (N, N- diethylamino) phenyl Amino) aryl；(N, the N- bis- such as 4- (N, N- dimethylamino) aminomethyl phenyl, 4- [2- (N, N- dimethylamino) ethyl] phenyl Alkyl amino) alkylaryl；3- (1- pyrrolidinyl) propyl, 3- (1- piperidyl) propyl, 3- (1- imidazole radicals) propyl etc. are by ring The alkyl that shape amino replaces；4- (1- pyrrolidinyl) phenyl, 4- (1- piperidyl) phenyl, 4- (1- imidazole radicals) phenyl etc. are cyclic annular The aryl that amino replaces；4- [2- (1- pyrrolidinyl) ethyl] phenyl, 4- [2- (1- piperidyl) ethyl] phenyl, 4- [2- (1- miaow Oxazolyl) ethyl] alkylaryl that is replaced by cyclic amino such as phenyl.
Alkyl obtained from being substituted as 1 or more hydrogen atom by oxyl, it can be cited for example that methoxy, second The alkoxyalkyls such as oxygroup methyl, methoxy ethyl, ethoxyethyl group.
Alkyl obtained from being substituted as 1 or more hydrogen atom by trialkylsilkl, it can be cited for example that front three The trialkylsilylalkyls such as base silyl methyl, 2- trimethylsilyethyl, 3- trimethylsilylpropyl.
Alkyl obtained from being substituted as 1 or more hydrogen atom by trialkoxysilyl, it can be cited for example that three The tri-alkoxies first such as methoxysilyl methyl, 2- trimethoxysilylethylgroup group, 3- trimethoxy-silylpropyl Arylalkoxysiloxyalkyl.
As the optional alkyl with substituent group, preferably carbon atom number is 1 or more and 20 below optionally with substitution The alkyl of base, more preferably carbon atom number be 1 or more and 20 alkyl below, further preferably carbon atom number be 1 or more and 10 alkyl below are still more preferably methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl or tertiary fourth Base, particularly preferably methyl or ethyl.
As R21And R22In trihydrocarbylsilyl groups, it can be cited for example that trimethyl silyl, triethyl-silicane Base, tripropylsilyl base, triisopropylsilyl, tributylsilyl, three amyl silicyls, three hexyl monosilanes The trialkylsilkls such as base, t-butyldimethylsilyl, preferably trimethyl silyl or triethylsilyl.
R21In a part and R22In a part bonding obtained from optionally with the Asia of nitrogen-atoms and/or oxygen atom Alkyl refers to alkylene or the alkylene with nitrogen-atoms and/or oxygen atom.
As alkylene, it can be cited for example that alkylidene, alkene diyl, arlydene, arlydene and alkylene and obtain Group (hereinafter sometimes referred to arylene-alkylene) arrived etc..As alkylidene, it can be cited for example that methylene, ethylidene, Asia Propyl, tetramethylene, pentamethylene, hexa-methylene, heptamethylene, eight methylene and 2,2,4- trimethyl hex- 1,6- diyl.Make For alkene diyl, it can be cited for example that amyl- 2- alkene -1,5- diyl.As arlydene, it can be cited for example that phenylene, naphthylene And biphenylene.As arylene-alkylene, it can be cited for example that phenylene-alkylidene, naphthylene-alkylidene and sub- biphenyl Base-alkylidene.As alkylene, preferably alkylidene, more preferably carbon atom number is 4 or more and 7 alkylidenes below.
As the alkylene with nitrogen-atoms and/or oxygen atom, it can be cited for example that base shown in-CH=N-CH=CH- Group ,-CH=N-CH2-CH2Shown in group ,-CH2-CH2-O-CH2-CH2Shown in group etc., preferably-CH=N-CH2- CH2Or-CH2-CH2-O-CH2-CH2Shown in group.
As the alkylene optionally with nitrogen-atoms and/or oxygen atom, preferably carbon atom number is 3 or more and 20 below The optionally alkylene with nitrogen-atoms and/or oxygen atom, preferably carbon atom number are 3 or more and 20 alkylene below, more excellent Being selected as carbon atom number is 4 or more and 7 alkylidenes below, further preferably tetramethylene, pentamethylene or hexa-methylene.
As R21In a part and R22In a part bonding obtained from-Si (R35)2-(CH2)x-Si(R35)2Institute The carbon atom number shown is 5 or more and 20 group (R below35Indicate that alkyl, x indicate 1 or more and 10 integers below), Ke Yiju - Si (CH out3)2-CH2-CH2-Si(CH3)2Shown in group etc..
As R21In a part and R22In a part bonding obtained from-Si (R36)2-(CH2)yShown in carbon it is former Subnumber is 4 or more and 20 group (R below36Indicate that alkyl, y indicate 2 or more and 11 integers below) ,-Si can be enumerated (CH3)2-CH2-CH2-CH2Shown in group etc..
R21And R22It is preferred that each independently representing alkyl or indicating R21In a part and R22In a part bonding Obtained from alkylene, more preferably each independently indicate carbon atom number be 1 or more and 4 alkyl below or indicate R21In A part and R22In a part bonding obtained from carbon atom number be 4 or more and 7 alkylidenes below, it is further preferably each From independently indicating that carbon atom number is 1 or more and 4 alkyl below, methyl or second are still more preferably each independently represented Base.
As the organic alkali metal compound with group shown in formula (2), specifically, dimethylamino can be enumerated Propyl lithium, diethyl amino propyl lithium, t-butyldimethylsilyloxy base propyl lithium, N- morphoinopropyl lithium, hexa-methylene Imine lithium, pyrrolidines lithium, piperidines lithium, heptamethylene imine lithium, ten dimethylene imine lithiums etc..
As the manufacturing method of the organic alkali metal compound with group shown in formula (2), can enumerate using formula (3) The method of compound represented reacts organic alkali metal compound with the secondary amine compound with group shown in formula (2) Method etc..
[changing 2]
。
In formula (3), R21And R22Respectively with the R in formula (2)21And R22It is synonymous, R31Indicate that carbon atom number is 6 or more and 100 Alkylene below, M indicate alkali metal atom.
R31Carbon atom number be 6 or more and 100 alkylene below be preferably carbon atom number be 7 or more and 90 Asias below Alkyl, more preferably carbon atom number are 8 or more and 80 alkylene below.
R31Carbon atom number be 8 or more and 80 alkylene below be preferably group shown in formula (3-1).
[changing 3]
。
In formula (3-1), R34It indicates the structural unit for being originated from conjugated diene compound and/or is originated from aromatic vinyl compound Structural unit, i and f indicate 1 or more and 10 integers below.It should be noted that in formula (3-1)-(CH2)iWith the nitrogen of formula (3) Atomistic binding, R34It is bonded with the M of formula (3).
As R34In the structural unit from conjugated diene compound and/or the structure from aromatic vinyl compound Unit is preferably derived from the structural unit, the structural unit from styrene or the structure list from butadiene of isoprene Member.
As the integer below of f, preferably 1 or more and 5.
As the integer below of i, preferably 2 or more and 4, it is more preferably 3.
As group, preferably R shown in above-mentioned formula (3-1)34For the structural unit from isoprene and base that i is 1 Group；R34Indicate the group that the structural unit for being originated from isoprene and i are 2；Or R34Indicate be originated from isoprene structural unit, And the group that i is 3.
As the alkali metal atom of M, it can be cited for example that lithium, sodium, potassium and caesium, preferably lithium.
Among formula (3) compound represented, as R31Group, R shown in expression (3-1)21And R22Table each independently Show alkyl and M indicates the compound of lithium, can enumerate makes (dialkyl amido) alkyl lithium compounds react and obtain with isoprene The compound arrived.As such compound, it can be cited for example that 3- (dimethylamino) propyl lithium, 3- (diethylamino) third Base lithium, 3- (dibutylamino) propyl lithium, 4- (dimethylamino) butyl lithium, 4- (diethylamino) butyl lithium, 4- (dipropyl Amino) butyl lithium, 3- (dibutylamino) butyl lithium etc..
Among formula (3) compound represented, as R31Group, R shown in expression (3-1)21And R22Indicate R21In one Part and R22In a part bonding obtained from alkylene and M indicate the compound of lithium, can enumerate makes with cyclic amino Alkyl lithium compounds reacted with isoprene obtained from compound.It, can as the alkyl lithium compounds with cyclic amino To enumerate 3- (1- pyrrolidinyl) propyl lithium, 3- (1- piperidyl) propyl lithium, 3- (1- hexamethyleneimino) propyl lithium, 3- [1- (1,2,3,6- tetrahydro pyridyl)] propyl lithium etc..
Among formula (3) compound represented, as R31Group, R shown in expression (3-1)21And R22Indicate R21In one Part and R22In a part bonding obtained from alkylene and M with nitrogen-atoms and/or oxygen atom indicate the chemical combination of lithium Object can enumerate compound obtained from making to have the alkyl lithium compounds of cyclic amino to react with isoprene etc..As tool Have the alkyl lithium compounds of cyclic amino, can enumerate 3- (1- morpholino) propyl lithium, 3- (1- imidazole radicals) propyl lithium, 3- (4, 5- dihydro -1- imidazole radicals) propyl lithium etc..
Among formula (3) compound represented, as R31Group, R shown in expression (3-1)21And R22Indicate R21In one Part and R22In a part bonding obtained from-Si (R35)2-(CH2)x-Si(R35)2Shown in carbon atom number be 5 or more and 20 group (R below35Indicate alkyl, x be 1 or more and 10 integers below) and M indicate lithium compound, can enumerate makes 3- (two sila -1- cyclopenta of 2,2,5,5- tetramethyl -1- azepine -2,5-) propyl lithium and isoprene, butadiene or styrene Compound obtained from reaction etc..
Among formula (3) compound represented, as R31Group, R shown in expression (3-1)21And R22Indicate R21In one Part and R22In a part bonding obtained from-Si (R36)2-(CH2)yShown in carbon atom number be 4 or more and 20 below Group (R36Indicate alkyl, y be 2 or more and 11 integers below) and M indicate lithium compound, 3- (2,2 ,-two can be enumerated Methyl-1-azepine-2- sila-1- cyclopenta) propyl lithium reacted with isoprene, butadiene or styrene obtained from compound Deng.
As formula (3) compound represented, preferably R31Group, R shown in expression (3-1)21And R22Each independently It indicates alkyl and M indicates the compound of lithium, more preferably R21And R22Each independently represent carbon atom number be 1 or more and 4 with Under alkyl, M indicate lithium, R31For group shown in formula (3-1), the R in formula (3-1)34Indicate the structure list for being originated from isoprene Member, f is 1 or more and 5 or less and i is 2 or more and 4 or less compounds, further preferably makes 3- (dimethylamino) propyl lithium Or 3- (diethylamino) propyl lithium reacted with isoprene obtained from compound.
Two or more can be applied in combination in formula (3) compound represented.
As polymerization initiator, the conjugated diene polymer of active end can be used.Active end Conjugated diene polymer can be such that polymerization initiator obtains with the monomer reaction comprising conjugated diene compound.As polymerization Substance identical with above compound can be used in initiator.Used in the conjugated diene polymer of active end Monomer is not particularly limited, as the monomer, can be used for example above-mentioned conjugated diene compound, aromatic vinyl compound, With the compound that can be copolymerized with conjugated diene compound.The conjugated diene polymer of active end is preferably only comprising different Pentadiene or comprising isoprene and aromatic vinyl compound as monomeric unit.
The usage amount of polymerization initiator used in the polymerization of monomer is preferably relative to the total amount 100g of monomer 0.01mmol~15mmol。
(solvent)
The polymerization of above-mentioned steps 1,1' and 1'' preferably carries out in a solvent.As solvent, as long as using not to above-mentioned steps 1,1' Or the polymerization of 1'' causes the substance hindered, preferably hydrocarbon solvent.
As hydrocarbon solvent, aliphatic hydrocarbon, aromatic hydrocarbon, clicyclic hydrocarbon etc. can be used.As aliphatic hydrocarbon, example can be enumerated Such as propane, normal butane, iso-butane, pentane, isopentane, n-hexane, propylene, 1- butylene, isobutene, trans-2-butene, suitable Formula -2- butylene, 1- amylene, 2- amylene, 1- hexene and 2- hexene.In addition, as aromatic hydrocarbon, it can be cited for example that benzene, toluene, two Toluene and ethylo benzene.As clicyclic hydrocarbon, it can be cited for example that pentamethylene and hexamethylene.Hydrocarbon solvent can be used alone, Two or more can be applied in combination.As hydrocarbon solvent, the mixed of aliphatic hydrocarbon as industrial hexane and clicyclic hydrocarbon can be used Close object.
(polymerization)
When carrying out the polymerization of monomer in solvent, the concentration of the monomer in solvent is usually 1 ~ 50 mass %, preferably 5 ~ 30 mass %.
Polymerization temperature is usually 25 ~ 100 DEG C, preferably 35 ~ 90 DEG C, more preferably 50 ~ 80 DEG C.Polymerization time is usually 10 Minute ~ 5 hours.
(modifying agent)
As modifying agent involved in present embodiment, the change with silicon atom, tin atom, germanium atom or phosphorus atoms can be used Close object.Modifying agent is preferably comprised with the functional group that can react with the reactive terminal of conjugated diene polymer and/or can With the compound of the functional group of conjugated diene compound copolymerization.Two or more can be applied in combination in these modifying agent.
Modifying agent may include the compound with structure shown in formula (5).
[changing 4]
。
In formula (5), R1Indicate alkyl, alkenyl, cycloalkenyl or aryl, M1Indicate that silicon atom, tin atom, germanium atom or phosphorus are former Son, L1Indicate halogen atom or oxyl, R1And L1There are it is multiple when, respectively can be identical or different, M1It is former for silicon atom, tin When son or germanium atom, n indicates that 0, m and l each independently represents 0 ~ 4 integer for meeting m+l=4, M1When for phosphorus atoms, n 0 Or 1, m and l each independently represent 0 ~ 3 integer for meeting m+l=3.
As R1In alkyl, preferably carbon atom number be 1 ~ 12 alkyl, it can be cited for example that methyl, ethyl, positive third Base, isopropyl, normal-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, dodecyl, cyclopenta and hexamethylene Base.As alkenyl, preferably carbon atom number be 2 ~ 12 alkenyl, it can be cited for example that vinyl, allyl, 1- acrylic and different Acrylic.As aryl, preferably carbon atom number be 6 ~ 12 aryl, it can be cited for example that phenyl, aminomethyl phenyl, ethylo benzene Base, benzyl, tolyl and xylyl.
As L1In halogen atom, it can be cited for example that chlorine atom, bromine atom and iodine atom.It, can be with as oxyl Enumerate such as alkoxy and aryloxy group.As alkoxy, preferably carbon atom number be 1 ~ 12 alkoxy, it can be cited for example that first Oxygroup, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amoxy, hexyloxy, oxygroup in heptan And octyloxy.As aryloxy group, preferably carbon atom number be 6 ~ 12 aryloxy group, it can be cited for example that phenoxy group and benzene methoxy Base.
As the compound with structure shown in formula (5), it can be cited for example that M1Silane compound, M for silicon atom1 Tin compound, M for tin atom1For the germanium compound and M of germanium atom1For the phosphorus compound of phosphorus atoms.
As silane compound, it can be cited for example that silicon tetrachloride, silicon bromide, silicon tetraiodide, methyl trichlorosilane, two Dimethyl dichlorosilane (DMCS), ethyl trichlorosilane, butyl trichlorosilane, hexyl trichlorosilane, tetramethoxy-silicane, methyl trimethoxy oxygroup Silane, dimethoxydimethylsilane, chlorine trimethoxy silane, methyltriethoxysilane, ethyl trimethoxy silane, diformazan Oxygroup diethylsilane, di ethoxy di methyl-monosilane, tetraethoxysilane, ethyl triethoxysilane, diethoxy diethyl Base silane, dichloro dimethoxysilane and trichloromethoxy silane.
As tin compound, it can be cited for example that tin tetrachloride, monomethyl trichlorine tin, Dan Yiji trichlorine tin, monobutyl three Chlorine tin, single phenyl trichlorine tin, tetramethoxy tin and tin tetraethoxide.
As germanium compound, it can be cited for example that germanium tetrachloride, germanium tetrabromide, germanium tetraiodide, methyl trichlorine germanium, ethyl three Chlorine germanium, phenyl trichlorine germanium, dimethyl anium dichloride, diethyl anium dichloride, dibutyl anium dichloride, diphenyl anium dichloride, tetramethoxy Germanium, tetraethoxy germanium, tetraisopropoxide germanium and four butoxy germanium.
As phosphorus compound, it can be cited for example that the halogenations such as phosphorus trichloride, phosphorus tribromide phosphorus compound, three nonyl of phosphorous acid The phosphoric acid such as the bi-ester of phosphite such as phenylester, Trimethyl phosphite, triethyl phosphite, trimethyl phosphate, triethyl phosphate Ester compounds.
Modifying agent may include the compound with structure shown in formula (6).
[changing 5]
。
In formula (6), X1、X2And X3Each independently represent alkyl, oxyl, halogen atom or can be with conjugated diene The functional group of the reactive terminal reaction of polymer, R61And R62Each independently represent hydrogen atom or alkyl, R61And R62There are multiple When, it respectively can be identical or different.A1Indicate have in oxygen atom, nitrogen-atoms, phosphorus atoms, sulphur atom and silicon atom extremely A kind of organic group of few atom is (comprising any one or more in oxygen atom, nitrogen-atoms, phosphorus atoms, sulphur atom or silicon atom Organic group), A1Optionally there is ring structure, X1、X2Or X3Structure in a part optionally and A1In a part bonding.That is, A1Optionally via X1、X2Or X3And with the silicon atom bonding in formula (6).A indicates 0 ~ 10 integer.
As X1、X2And X3In alkyl, it can be cited for example that alkyl, aryl, alkenyl and aralkyl.As alkyl, preferably The alkyl for being 1 ~ 12 for carbon atom number, it can be cited for example that methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tertiary fourth Base, n-pentyl, n-hexyl, n-octyl, dodecyl, cyclopenta and cyclohexyl.As aryl, preferably carbon atom number be 6 ~ 12 aryl, it can be cited for example that phenyl, aminomethyl phenyl, ethylphenyl, benzyl, tolyl and xylyl.As alkenyl, Preferably carbon atom number be 2 ~ 12 alkenyl, it can be cited for example that vinyl, allyl, 1- acrylic and isopropenyl.As Aralkyl, it can be cited for example that benzyl.
As oxyl, it can be cited for example that alkoxy, aryloxy group etc..As alkoxy, preferably carbon atom number be 1 ~ 12 alkoxy, it can be cited for example that methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, sec-butoxy and uncle Butoxy.As aryloxy group, preferably carbon atom number be 6 ~ 12 aryloxy group, it can be cited for example that phenoxy group and benzyloxy. As oxyl, preferably alkoxy, more preferably methoxy or ethoxy.
As halogen atom, it can be cited for example that chlorine atom, bromine atom and iodine atom.
As the functional group that can be reacted with the reactive terminal of conjugated diene polymer, it can be cited for example that having epoxy The alkyl of base and alkyl with carbonyl.
As R61And R62In alkyl, preferably carbon atom number be 1 ~ 4 alkyl, more preferably carbon atom number is 1 ~ 4 Alkyl, further preferably methyl or ethyl.R61There are it is multiple when, multiple R61It can be the same or different from each other, R62There are multiple When, multiple R62It can be the same or different from each other.
A is from the viewpoint of improving and saving burnup, and preferably 3 or more, from the viewpoint of economy when improving manufacture, Preferably 4 or less.
As at least with the organic group A of nitrogen-atoms1, it can be cited for example that group shown in formula (6-1).
[changing 6]
。
In formula (6-1), R63And R64Alkyl or trihydrocarbylsilyl groups optionally with substituent group is each independently represented, Or indicate R63In a part and R64In a part bonding obtained from optionally have be selected from silicon atom, nitrogen-atoms and oxygen The alkylene of at least one of atom atom.
Here, group shown in formula (6-1) is in R63In a part and R64In a part be not bonded in the case where be non- Cyclic amino, in R63With R64It is cyclic amino in the case where bonding.
R63And R64In optionally with substituent group alkyl be alkyl or substituted alkyl.
As alkyl, it can be cited for example that the carbon atom numbers such as methyl, ethyl, n-propyl, isopropyl, normal-butyl are 1 ~ 12 Alkyl；The alkenyl that the carbon atom numbers such as vinyl, allyl, isopropenyl are 2 ~ 12；The carbon atom numbers such as phenyl, benzyl are 6 ~ 12 Aryl, preferably alkyl or aryl, more preferably methyl, ethyl or benzyl.
As substituted alkyl, it can be cited for example that the oxacycloalkyls such as oxirane base, tetrahydrofuran base, preferably Tetrahydrofuran base.
In this specification, oxacycloalkyl indicates the CH on the alicyclic ring of naphthenic base2Group obtained from being substituted by oxygen atom.
As R63And R64In trihydrocarbylsilyl groups, it can be cited for example that trimethyl silyl, fert-butyidimethylsilyl Silicyl, preferably trimethyl silyl.
R63In a part and R64In a part bonding obtained from optionally have be selected from silicon atom, nitrogen-atoms and oxygen The alkylene of at least one of atom atom be alkylene or in silicon atom, nitrogen-atoms and oxygen atom at least A kind of alkylene of atom (containing heteroatomic alkylene).
As alkylene, it can be cited for example that tetramethylene, pentamethylene, hexa-methylene, 2,2,4- trimethyl hex- 1,6- The alkylidene that the carbon atom numbers such as diyl are 2 ~ 12, wherein preferably carbon atom number is 4 ~ 7 alkylidene, and particularly preferably five is sub- Methyl or hexa-methylene.
As contain heteroatomic alkylene, it can be cited for example that the alkylene of the alkylene of silicon atoms, nitrogen atom and Alkylene containing oxygen atom.
As the alkylene of silicon atoms, it can be cited for example that-Si (CH3)2-CH2-CH2-Si(CH3)2Shown in group. As the alkylene of nitrogen atom, it can be cited for example that group shown in-CH=N-CH=CH- and-CH=N-CH2-CH2Shown in Group.As the alkylene containing oxygen atom, it can be cited for example that-CH2-CH2-O-CH2-CH2Shown in group.
As at least with the organic group A of oxygen atom1, it can be cited for example that group shown in formula (6-2).
[changing 7]
。
In formula (6-2), X4Indicate the alkylene that optionally carbon atom number with oxygen atom is 1 ~ 6, R65Indicate hydrogen atom or The alkyl that carbon atom number is 1 ~ 6.
As X4In optionally with oxygen atom carbon atom number be 1 ~ 6 alkylene, it can be cited for example that unsubstituted Alkylene and alkylene with the group with oxygen atom as substituent group.
As X4, specifically, more specifically can enumerate alkylene and sub- oxyl can enumerate ethylidene, Asia Propyl, butylidene, 1- oxygroup ethylidene, 1- oxygroup trimethylene and 1- oxygroup tetramethylene.As X4, preferably 1- oxygroup three Methylene.
As R65In carbon atom number be 1 ~ 6 alkyl, it can be cited for example that alkyl and aryl, specifically, can lift Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, isopentyl, n-hexyl, ring out Hexyl and phenyl.As R65, preferably hydrogen atom or methyl.
As at least with the organic group A of sulphur atom1, it can be cited for example that group shown in formula (6-3).
[changing 8]
。
In formula (6-3), R66Indicate trihydrocarbylsilyl groups.As trihydrocarbylsilyl groups, trimethyl first silicon can be enumerated Alkyl, triethylsilyl, t-butyldimethylsilyl, preferably trimethyl silyl or triethyl-silicane Base.
As at least with the organic group A of silicon atom1, it can be cited for example that group shown in formula (6-4).That is, conduct Formula (6) compound represented, it can be cited for example that as A1And the polysiloxane chemical combination with group shown in formula (6-4) Object.
[changing 9]
。
In formula (6-4), R66、R67And R68Each independently represent the base of alkyl or the repetitive unit with sub- oxyl Group, X5And X6Each independently represent group, halogen atom or the energy of alkyl, oxyl, repetitive unit with sub- oxyl Enough functional groups reacted with the reactive terminal of conjugated diene polymer, g indicate 0 ~ 600 integer, and there are multiple R66And X5 There are it is multiple when, respectively can be identical or different.
As R66、R67、R68、X5And X6In alkyl, it can be cited for example that alkyl, aryl and aralkyl.It is excellent as alkyl It is selected as the alkyl that carbon atom number is 1 ~ 12, it can be cited for example that methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, uncle Butyl, n-pentyl, n-hexyl, n-octyl, dodecyl, cyclopenta and cyclohexyl.As aryl, preferably carbon atom number is 6 ~ 12 aryl, it can be cited for example that phenyl, aminomethyl phenyl, ethylphenyl, tolyl and xylyl.It is excellent as aralkyl It is selected as the aralkyl that carbon atom number is 7 ~ 13, it can be cited for example that benzyl.
As R66、R67、R68、X5And X6In the repetitive unit with sub- oxyl group, it can be cited for example that having The group of repetitive unit based on aklylene glycol.As sub- oxyl, it can be cited for example that 1- oxygroup ethylidene, 1- oxygroup three Methylene and 1- oxygroup tetramethylene, preferably 1- oxygroup ethylidene.
As X5And X6In oxyl, it can be cited for example that alkoxy and aryloxy group.As alkoxy, preferably carbon is former The alkoxy that subnumber is 1 ~ 12, it can be cited for example that methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, Zhong Ding Oxygroup, tert-butoxy, amoxy, hexyloxy, oxygroup in heptan and octyloxy.As aryloxy group, preferably carbon atom number is 6 ~ 12 Aryloxy group, it can be cited for example that phenoxy group and benzyloxy.
As halogen atom, it can be cited for example that chlorine atom, bromine atom and iodine atom.
As the functional group that can be reacted with the reactive terminal of conjugated diene polymer, it can be cited for example that having epoxy The alkyl of base and alkyl with carbonyl.
G is from the viewpoint of processing, and preferably 3 ~ 360, from the viewpoint of saving burnup performance, preferably 4 ~ 20.
Among compound with structure shown in formula (6), as A1For the chemical combination of acyclic amino group shown in formula (6-1) Object, it can be cited for example that [3- (dimethylamino) propyl] trimethoxy silane, [3- (diethylamino) propyl] trimethoxy Silane, [3- (dimethylamino) propyl] triethoxysilane, [3- (diethylamino) propyl] triethoxysilane, [3- (second Vlmethyl) propyl] trimethoxy silane, [3- (ethylmethylamino) propyl] triethoxysilane, [3- (dimethylamino Base) propyl] methyl dimethoxysilane, [3- (diethylamino) propyl] methyl dimethoxysilane, [3- (dimethylamino) Propyl] ethyldimethoxysilane, [3- (diethylamino) propyl] ethyldimethoxysilane, [3- (dimethylamino) third Base] dimethyl methoxy silane, [3- (dimethylamino) propyl] methyldiethoxysilane, [3- (diethylamino) propyl] Methyldiethoxysilane, [3- (dimethylamino) propyl] ethyl diethoxy silane, [3- (diethylamino) propyl] second Base diethoxy silane, [3- (ethylmethylamino) propyl] methyldiethoxysilane, [3- (ethylmethylamino) propyl] Ethyl diethoxy silane, [3- (N- allyl N- methylamino) amyl] trimethoxy silane, [3- (N- benzyl N- methyl Amino) propyl] trimethoxy silane, [3- (N- benzyl N- methylamino) propyl] triethoxysilane, [3- (N- phenyl N- Propylcarbamic) amyl] trimethoxy silane, { 3- [two (methoxy) amino] propyl } trimethoxy silane, { 3- [two (first Oxygroup ethyl) amino] propyl } trimethoxy silane, { 3- [two (methoxy) amino] propyl } triethoxysilane, { 3- [two (methoxy ethyl) amino] propyl } triethoxysilane, { 3- [two (ethoxyethyl group) amino] propyl } trimethoxy silicon Alkane, { 3- [two (ethoxyl methyl) amino] propyl } trimethoxy silane, 3- [two (ethoxyethyl group) amino] propyl] three second Oxysilane, { 3- [two (ethoxyl methyl) amino] propyl } triethoxysilane, { 3- [N, N- bis- (trimethyl silyls) Amino] propyl } trimethoxy silane, { 3- [bis- (trimethyl silyl) amino of N, N-] propyl } triethoxysilane, { 3- [bis- (t-butyldimethylsilyl) amino of N, N-] propyl } trimethoxy silane, the { 3- [bis- (tertbutyldimethylsilyl chlorides of N, N- Silylation) amino] propyl } triethoxysilane, { 3- [bis- (trimethyl silyl) amino of N, N-] propyl } methyl dimethoxy oxygen Base silane, { 3- [bis- (trimethyl silyl) amino of N, N-] propyl } methyldiethoxysilane, the { 3- [bis- (tert-butyls of N, N- Dimetylsilyl) amino] propyl } methyl dimethoxysilane, { 3- [bis- (t-butyldimethylsilyl) ammonia of N, N- Base] propyl } methyldiethoxysilane, { 3- [bis- (trimethyl silyl) amino of N, N-] propyl } dimethyl methyl oxygroup silicon Alkane, [3- (ethylmethylamino) propyl] trimethoxy silane, [3- (ethylmethylamino) propyl] triethoxysilane, [3- (ethylmethylamino) propyl] methyl dimethoxysilane, [3- (ethylmethylamino) propyl] ethyldimethoxysilane, [3- (ethylmethylamino) propyl] methyldiethoxysilane and [3- (ethylmethylamino) propyl] ethyl diethoxy silicon Alkane.
Among compound with structure shown in formula (6), as A1For the chemical combination of acyclic amino group shown in formula (6-1) Object, from the viewpoint of improving and saving burnup, preferably [3- (dimethylamino) propyl] trimethoxy silane, [3- (diethyl Amino) propyl] trimethoxy silane, [3- (dimethylamino) propyl] triethoxysilane or [3- (diethylamino) propyl] Triethoxysilane.
Among compound with structure shown in formula (6), as A1For the chemical combination of cyclic amino shown in formula (6-1) Object, it can be cited for example that 3- morphoinopropyl trimethoxy silane, 3- morphoinopropyl triethoxysilane, 3- morphoinopropyl Methyl dimethoxysilane, 3- morphoinopropyl ethyldimethoxysilane, 3- morphoinopropyl methyldiethoxysilane, 3- Morphoinopropyl ethyl diethoxy silane, 3- piperidino propyl trimethoxy silicane, 3- piperidino propyl triethoxy Silane, 3- piperidino hydroxypropyl methyl dimethoxysilane, 3- piperidino ethyl dimethoxysilane, 3- piperidino Hydroxypropyl methyl diethoxy silane, 3- piperidino ethyl diethoxy silane, N- (3- trimethoxysilyl third Base) -4,5- glyoxalidine, N- (3- triethoxysilylpropyltetrasulfide) -4,5- glyoxalidine, N- (3- trimethyoxysilane Base propyl) -4,5- imidazoles, N- (3- triethoxysilylpropyltetrasulfide) -4,5- imidazoles, 3- hexamethyleneimino propyl front three Oxysilane, 3- hexamethyleneimino propyl-triethoxysilicane, 3- hexamethyleneimino hydroxypropyl methyl dimethoxy silicon Alkane, 3- hexamethyleneimino ethyl dimethoxysilane, 3- hexamethyleneimino hydroxypropyl methyl diethoxy silane With 3- hexamethyleneimino ethyl diethoxy silane.
Among compound with structure shown in formula (6), as A1For the chemical combination of cyclic amino shown in formula (6-1) Object, from the viewpoint of improving and saving burnup, preferably N- (3- trimethoxy-silylpropyl) -4,5- glyoxalidine, N- (3- triethoxysilylpropyltetrasulfide) -4,5- glyoxalidine, N- (3- trimethoxy-silylpropyl) -4,5- imidazoles or N- (3- triethoxysilylpropyltetrasulfide) -4,5- imidazoles.
Among compound with structure shown in formula (6), as A1It, can for the compound of group shown in formula (6-2) To enumerate such as 3- glycidoxypropyltrime,hoxysilane, 3- epoxy propoxy propyl triethoxysilane, 3- epoxy third Oxygroup hydroxypropyl methyl dimethoxysilane, 3- glycidoxypropyl group ethyldimethoxysilane, 3- glycidoxypropyl group first Base diethoxy silane, 3- glycidoxypropyl group ethyl diethoxy silane, bis- (3- glycidoxypropyl group) dimethoxys Silane and bis- (3- glycidoxypropyl group) diethoxy silanes.
Among compound with structure shown in formula (6), as A1For the compound of group shown in formula (6-2), from It improves from the perspective of saving the viewpoint of burnup, the acquisition easiness for improving compound, long-term storing stability, preferably 3- ring Oxygen propoxypropyl trimethoxy silane.
Among compound with structure shown in formula (6), as A1It, can for the compound of group shown in formula (6-3) To enumerate such as S- trimethyl silyl mercaptopropyi trimethoxy silane, three ethoxy of S- trimethyl silyl mercaptopropyi Base silane, S- trimethyl silyl mercapto propyl methyl dimethoxy silane, S- trimethyl silyl mercaptopropyi methyl Diethoxy silane, S- triethylsilyl mercaptopropyi trimethoxy silane, S- triethylsilyl mercaptopropyi three Ethoxysilane, S- triethylsilyl mercapto propyl methyl dimethoxy silane and S- triethylsilyl mercaptopropyi Methyldiethoxysilane.
Among compound with structure shown in formula (6), as A1It, can for the compound of group shown in formula (6-4) With enumerate such as diepoxy propoxyl group dimethyl silicone polymer, dimethyl (methoxymethyl siloxanes) dimethyl silicone polymer, Dimethyl (acetoxy-methyl siloxanes) dimethyl silicone polymer, 2-glycidyl based polysiloxane and dichloro poly dimethyl Siloxanes.
As the compound with structure shown in formula (6) in addition to the above compounds, it can be cited for example that three [3- (trimethoxysilyl) propyl] isocyanuric acid ester, three [3- (triethoxysilyl) propyl] isocyanuric acid esters, three [3- (tripropoxy-silicane base) propyl] isocyanuric acid ester, three [3- (three butoxy silicyls) propyl] isocyanuric acid esters etc. Three [(alkoxysilyl) alkyl] isocyanurate compounds.Wherein, as formula (6) compound represented, preferably three [3- (trialkoxysilyl) propyl] isocyanuric acid ester, more preferably alkoxy is the alkoxy that carbon atom number is 1 ~ 4 Three [3- (trialkoxysilyl) propyl] isocyanuric acid esters, further preferably three [3- (trimethoxysilyl) third Base] isocyanuric acid ester.
As the compound with structure shown in formula (6) in addition to the above compounds, it can be cited for example that bis- (three Chlorosilyl) methane, bis- (silicochloroform base) ethane of 1,2-, bis- (silicochloroform base) propane of 1,3-, the bis- (trichlorines of 1,4- Silicyl) butane, bis- (silicochloroform base) pentanes of 1,5-, bis- (silicochloroform base) hexanes of 1,6-, bis- (trimethoxy first Silylation) methane, bis- (triethoxysilyl) methane, bis- (trimethoxysilyl) ethane, bis- (triethoxy first silicon Alkyl) ethane, bis- (trimethoxysilyl) propane, bis- (triethoxysilyl) propane, bis- (trimethyoxysilanes Base) butane, bis- (triethoxysilyl) butane, bis- (trimethoxysilyl) heptane, bis- (triethoxy-silicanes Base) heptane, bis- (trimethoxysilyl) hexanes, bis- (triethoxysilyl) hexanes, bis- (trimethyoxysilanes Base) benzene, bis- (triethoxysilyl) benzene, bis- (trimethoxysilyl) hexamethylenes, bis- (triethoxysilyls) Hexamethylene, bis- (triethoxysilyl) benzene, bis- (trimethoxysilyl) octanes, bis- (triethoxysilyls) are pungent Alkane, bis- (trimethoxysilyl) nonanes, bis- (triethoxysilyl) nonanes, bis- (trimethoxysilyl) second Alkene, bis- (triethoxysilyl) ethylene, bis- (trimethoxysilylethylgroup group) benzene, bis- (triethoxysilyl second Base) benzene, bis- (3- trimethoxy-silylpropyl) ethane, bis- (3- triethoxysilylpropyltetrasulfide) ethane, 3- aminopropan Base trimethoxy silane, 3-aminopropyltriethoxysilane, 3- mercapto methyl trimethoxy silane, three ethoxy of 3- mercapto methyl Base silane, 3-mercaptopropyi trimethoxy silane, 3- Mercaptopropyltriethoxysilane, aminophenyl trimethoxy silane, ammonia Base phenyl triethoxysilane, 3- (N- methylamino) propyl trimethoxy silicane, 3- (N- methylamino) propyl triethoxy Silane, N- (2- amino-ethyl) -3- TSL 8330,2- (6- Aminohexyl) aminopropyl trimethoxy silicon Alkane, three ethoxy of 3- [N-2- { bis- (trimethyl silyl) amino of N', N'- } ethyl-N- trimethyl silyl amino] propyl Base silane, 3- [N-2- { bis- (triethylsilyl) amino of N', N'- } ethyl-N- triethylsilyl amino] propyl three Ethoxysilane, 3- [N-2- { bis- (triethylsilyl) amino of N', N'- } ethyl-N- triethylsilyl amino] third Base trichlorosilane, N- (3- trimethoxy-silylpropyl) -4- methylpentane -2- imines, N- (3- triethoxysilyl Propyl) -4- methylpentane -2- imines, N- (3- triethoxysilylpropyltetrasulfide) propane -2- imines, N- (3- triethoxy first Ethoxysilylpropyl) pentane -3- imines, N- (3- silicochloroform base propyl) -4- methylpentane -2- imines, the bis- [3- (three of 1,4- Methoxysilyl) propyl] piperazine, 1,4- bis- [3- (triethoxysilyl) propyl] piperazines, bis- [3- (trimethoxies Silicyl) propyl]-N- trimethyl silyl amine, bis- [3- (triethoxysilyl) propyl]-N- trimethyl silyls It is base amine, bis- [3- (trimethoxysilyl) propyl] methyl amines, bis- [3- (triethoxysilyl) propyl] methyl amines, double [3- (trimethoxysilyl) propyl] ethylamine, bis- [3- (triethoxysilyl) propyl] ethylamines, three (trimethoxies Base silyl methyl) amine, three (triethoxysilylmethyl) amine, 2,2- dimethoxy -1- phenyl -1- azepine -2- silicon Heterocycle pentane, 2,2- diethoxy -1- phenyl -1- azepine -2- silacyclopentan, 2,2- dimethoxy -1- butyl -1- azepine - 2- silacyclopentan, 2,2- diethoxy -1- butyl -1- azepine -2- silacyclopentan, 2,2- dimethoxy -1- trimethyl first Silylation -1- azepine -2- silacyclopentan, 2,2- dimethoxy -1- (3- trimethoxy-silylpropyl) -1- azepine -2- Silacyclopentan, 2,2- diethoxy -1- (3- triethoxysilylpropyltetrasulfide) -1- azepine -2- silacyclopentan, 2,2- bis- Methoxyl group -8- (4- methyl piperidine base) methyl-1,6- dioxa -2- sila cyclooctane, 2,2- diethoxy -8- (4- methyl piperazine Piperidinyl) methyl-1,6- dioxa -2- sila cyclooctane, 2,2- dimethoxy -8- (N, N- diethyl) methyl-1,6- dioxa - 2- sila cyclooctane, 2- methoxyl group -2- methyl -8- (4- methyl piperidine base) methyl-1,6- dioxa -2- sila cyclooctane, 2, The chloro- 8- of 2- bis- (4- methyl piperidine base) methyl-1,6- dioxa -2- sila cyclooctane, N- [2- (trimethoxysilyl) - Ethyl]-N, N', N'- Trimethylethane -1,2- diamines, 2- [3- (trimethoxysilyl) propyl] -1,3- methylimidazole Alkane and 2- [3- (trimethoxysilyl) propyl] -1,3- (double trimethyl silyls) imidazolidine.
Modifying agent may include the compound with structure shown in formula (7).
[changing 10]
。
In formula (7), R71Indicate that hydrogen atom or alkyl, s indicate 0 or 1 (0 ~ 1 integer), R72Indicate alkylene, X7、X8With X9Each independently represent substituted amino or optionally with the alkyl of substituent group, X7、X8And X9In at least one be replace Amino.
As R71In alkyl, it can be cited for example that alkyl, alkenyl and aryl.
As alkyl, preferably carbon atom number be 1 ~ 12 alkyl, it can be cited for example that methyl, ethyl, n-propyl, isopropyl Base, normal-butyl, sec-butyl and tert-butyl, preferably methyl.As alkenyl, preferably carbon atom number be 2 ~ 12 alkenyl, can be with Enumerate such as vinyl, allyl, 1- acrylic and isopropenyl, preferably vinyl.As aryl, preferably carbon atom number For 6 ~ 12 aryl, it can be cited for example that phenyl, aminomethyl phenyl and ethylphenyl, preferably phenyl.
As R71, preferably hydrogen atom, methyl, vinyl or phenyl, more preferably hydrogen atom.
As R72In alkylene, it can be cited for example that alkylidene, arlydene and arlydene and alkylene and obtain Group.
As alkylidene, preferably carbon atom number be 2 ~ 6 alkylidene, it can be cited for example that methylene, ethylidene and three Methylene, further preferably methylene or ethylidene.As arlydene, preferably carbon atom number is 5 ~ 12 arlydene, can To enumerate such as phenylene, naphthylene and biphenylene, further preferably phenylene.As arlydene and alkylene Obtained group, it can be cited for example that group, naphthylene and alkylene obtained from phenylene and alkylene and obtain Group obtained from the group and biphenylene and alkylene that arrive, preferably base obtained from phenylene and alkylene Group.
As group, the preferably R of formula (7) obtained from arlydene and alkylene71The carbon atom that is bonded with should The carbon atom bonding of the arlydene of group.
As group (phenylene-alkylidene) obtained from phenylene and alkylene, it can be cited for example that formula (7-R) Shown in group.
[changing 11]
。
In formula, d indicates 1 ~ 10 integer.
As phenylene-alkylidene, the position for the carbon atom on phenyl ring being bonded according to alkylidene can be enumerated p- Phenylene-alkylidene ,-phenylene-alkylidene, o- phenylene-alkylidene.It is p- in the case where group shown in formula (7-R) Phenylene-alkylidene is group shown in formula (7-Ra), and-phenylene-alkylidene is group shown in formula (7-Rb), o- Asia Phenyl-alkylidene is group shown in formula (7-Rc).
[changing 12]
[changing 13]
[changing 14]
In formula, d1, d2 and d3 each independently represent 1 ~ 10 integer.
As group obtained from arlydene and alkylene, preferably base obtained from phenylene and alkylene Group's (phenylene-alkylidene), more preferably group shown in group or formula (7-Rb) shown in formula (7-Ra), further preferably P-phenylene-methylene (group shown in the formula (7-Ra) of d1=1) ,-phenylene-methylene (formula (7-Rb) institute of d2=1 The group shown), p-phenylene-ethylidene (group shown in the formula (7-Ra) of d1=2) or-phenylene-ethylidene (d2=2 Group shown in formula (7-Rb)).
As X7、X8And X9In optionally with substituent group alkyl, alkyl and substituted alkyl can be enumerated.
As X7、X8And X9Alkyl, it can be cited for example that alkyl, alkenyl, alkynyl, aryl and aralkyl.As alkyl, Preferably carbon atom number be 1 ~ 12 alkyl, it can be cited for example that methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl And tert-butyl.As alkenyl, preferably carbon atom number be 2 ~ 12 alkenyl, it can be cited for example that vinyl, allyl, 1- propylene Base and isopropenyl.As alkynyl, preferably carbon atom number is 2 ~ 12 alkynyl, can enumerate acetenyl and 2-propynyl.Make For aryl, preferably carbon atom number be 6 ~ 12 aryl, it can be cited for example that phenyl, tolyl and xylyl.As aralkyl The aralkyl that base, preferably carbon atom number are 7 ~ 13, it can be cited for example that benzyl.As alkyl, preferably alkyl.
As X7、X8And X9Substituted alkyl, can enumerate have in oxygen atom, nitrogen-atoms and silicon atom extremely A kind of group of few atom.
As the substituted alkyl with oxygen atom, it can be cited for example that methoxy, methoxy ethyl, (ethoxymethyl) The alkoxyalkyls such as base, ethoxyethyl group.
As the substituted alkyl with nitrogen-atoms, it can be cited for example that dimethylaminomethyl, dimethyl aminoethyl, The dialkyl aminoalkyls such as diethylamino methyl, diethylamino ethyl.
As the substituted alkyl with silicon atom, it can be cited for example that trimethylsilyl methyl, trimethyl first silicon The trialkylsilylalkyls such as alkyl ethyl, triethylsilylmethyl, triethylsilyl ethyl.
The carbon atom number of the optionally alkyl with substituent group is preferably 1 ~ 10, more preferably 1 ~ 4.Replace as optionally having The alkyl of base, preferably alkyl or alkoxyalkyl.As alkyl, further preferably carbon atom number be 1 ~ 4 alkyl, especially Preferably methyl or ethyl.As alkoxyalkyl, preferably carbon atom number be 2 ~ 4 alkoxyalkyl.
As X7、X8And X9In substituted amino, it can be cited for example that shown in group shown in formula (7-X) and formula (7-Y) Group.
[changing 15]
In formula (7-X), R73And R74Alkyl or trihydrocarbylsilyl groups are each independently represented, or indicate R73In a part With R74In a part bonding obtained from optionally with the alkylene of nitrogen-atoms and/or oxygen atom.
[changing 16]
In formula (7-Y), R75Indicate that hydrocarbon pitches base.It should be noted that R75It is R in formula (7-X)73And R74It is for a group and former with nitrogen Group corresponding to the group that son is bonded with double bond.
As R73And R74In alkyl, it can be cited for example that alkyl, alkenyl, alkynyl, aryl and aralkyl.As alkyl, Preferably carbon atom number be 1 ~ 12 alkyl, it can be cited for example that methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl And tert-butyl.As alkenyl, preferably carbon atom number be 2 ~ 12 alkenyl, it can be cited for example that vinyl, allyl, 1- propylene Base and isopropenyl.As alkynyl, preferably carbon atom number be 2 ~ 12 alkynyl, it can be cited for example that acetenyl and 2- propine Base.As aryl, preferably carbon atom number be 6 ~ 12 aryl, it can be cited for example that phenyl, tolyl and xylyl.As The aralkyl that aralkyl, preferably carbon atom number are 7 ~ 13, it can be cited for example that benzyl.
The carbon atom number of alkyl is preferably 1 ~ 10, more preferably 1 ~ 4, further preferably 1 ~ 2.As alkyl, preferably Alkyl, more preferably straight chained alkyl.
As R73And R74In trihydrocarbylsilyl groups, it can be cited for example that trimethyl silyl, triethyl-silicane The trialkylsilkl that the carbon atom numbers such as base, triisopropylsilyl, t-butyldimethylsilyl are 3 ~ 12.
As trihydrocarbylsilyl groups, preferably carbon atom number be 3 ~ 9 trialkylsilkl, more preferably with silicon original The alkyl that sub-key is closed is the trialkylsilkl for the alkyl that carbon atom number is 1 ~ 3, further preferably trimethyl silyl.
As R73In a part and R74In a part bonding obtained from optionally have nitrogen-atoms and/or oxygen atom Alkylene, it can be cited for example that the alkylene of alkylene, nitrogen atom and the alkylene containing oxygen atom.
As alkylene, it can be cited for example that the Asias such as ethylidene, trimethylene, tetramethylene, pentamethylene, hexa-methylene Alkyl.
As the alkylene of nitrogen atom, it can be cited for example that-CH2CH2-NH-CH2Shown in group ,-CH2CH2-N= Group and-CH shown in group ,-CH shown in CH-=CH-N=CH-2CH2-NH-CH2CH2Shown in group.
As the alkylene containing oxygen atom, it can be cited for example that-CH2CH2-O-CH2CH2Shown in group.
The carbon atom number of the optionally alkylene with nitrogen-atoms and/or oxygen atom is preferably 2 ~ 20, more preferably 2 ~ 7, into One step is preferably 4 ~ 6.
As optionally with the alkylene of nitrogen-atoms and/or oxygen atom, preferably alkylene, more preferably alkylidene, into One step is preferably polymethylene.
As R73And R74, preferably it is each independently alkyl or trialkylsilkl or R73In a part and R74 In a part bonding obtained from alkylidene, be more preferably each independently alkyl.
As group shown in formula (7-X), acyclic amino group or cyclic amino can be enumerated.
Among acyclic amino group, as R in formula (7-X)73And R74For the group of alkyl, it can be cited for example that dimethylamino Base, diethylamino, two (n-propyl) amino, two (isopropyl) amino, two (normal-butyl) amino, two (sec-butyl) amino, two The dialkyl amidos such as (tert-butyl) amino, ethylmethylamino.
Among acyclic amino group, as R in formula (7-X)73And R74For the group of trihydrocarbylsilyl groups, example can be enumerated Such as bis- (trimethyl silyl) amino, bis- (trialkylsilkl) ammonia of bis- (t-butyldimethylsilyl) amino Base.
Among cyclic amino, as R in formula (7-X)73In a part and R74In a part bonding obtained from group For the group of alkylene, it can be cited for example that 1- aziridine base, 1- azetidinyl, 1- pyrrolidinyl, 1- piperidyl, 1- hexamethyleneimino and 1- pyrrole radicals.
Among cyclic amino, as R in formula (7-X)73In a part and R74In a part bonding obtained from group For the group of the alkylene of nitrogen atom, it can be cited for example that 1- imidazole radicals, 4,5- dihydro -1- imidazole radicals, 1- imidazolidinyl, 1- Piperidyl.
Among cyclic amino, as R in formula (7-X)73In a part and R74In a part bonding obtained from group For the group of the alkylene containing oxygen atom, morpholino base can be enumerated.
As R75In hydrocarbon pitch base, it can be cited for example that ethidine, propylidene base, butane, 1- methyl ethidine, 1- methyl Propylidene base and 1,3- dimethyl butane.
The carbon atom number of hydrocarbon fork base is preferably 2 ~ 20, more preferably 2 ~ 6.
As group shown in formula (7-Y), it can be cited for example that ethidine amino, 1- methyl propylidene base amino, 1,3- bis- Methyl butane amino, 1- methyl ethidine amino, 4-N, the acyclic amino groups such as N- dimethylamino benzene methvleneamino.
In formula (7), X9、X9And X9In substituted amino be preferably acyclic amino group, more preferably dialkyl amido, into One step is preferably dimethylamino, diethylamino, two (n-propyl) amino or two (normal-butyl) amino, particularly preferably diformazan Base amino or diethylamino.
In formula (7), X7、X8And X9In at least one be replace amino, preferably X7、X8And X9In 2 the above are take The amino in generation, more preferably X7、X8And X9Among 2 be replace amino.
Among formula (7) compound represented, as R71For hydrogen atom and X7、X8And X9Among 1 be dialkyl amido Compound, following compounds can be enumerated.
The compound for being 0 as the s in formula (7), it can be cited for example that (dimethylamino) dimethylvinylsiloxy base silane, (diethylamino) dimethylvinylsiloxy base silane, (dipropylamino) dimethylvinylsiloxy base silane, (dibutylamino) dimethyl Vinyl silanes, (dimethylamino) diethyl vinyl silanes, (diethylamino) diethyl vinyl silanes, (dipropyl Amino) diethyl vinyl silanes and (dibutylamino) diethyl vinyl silanes.
The compound for being 1 as the s in formula (7), it can be cited for example that (dimethylamino) dimethyl (4- vinyl benzene Base) silane, (dimethylamino) dimethyl (3- ethenylphenyl) silane, (diethylamino) dimethyl (4- ethenylphenyl) Silane, (diethylamino) dimethyl (3- ethenylphenyl) silane, (dipropylamino) dimethyl (4- ethenylphenyl) silicon Alkane, (dipropylamino) dimethyl (3- ethenylphenyl) silane, (dibutylamino) dimethyl (4- ethenylphenyl) silane, (dibutylamino) dimethyl (3- ethenylphenyl) silane, (dimethylamino) diethyl (4- ethenylphenyl) silane, (two Methylamino) diethyl (3- ethenylphenyl) silane, (diethylamino) diethyl (4- ethenylphenyl) silane, (diethyl Base amino) diethyl (3- ethenylphenyl) silane, (dipropylamino) diethyl (4- ethenylphenyl) silane, (dipropyl Amino) diethyl (3- ethenylphenyl) silane, (dibutylamino) diethyl (4- ethenylphenyl) silane and (dibutylamine Base) diethyl (3- ethenylphenyl) silane.
Among formula (7) compound represented, as R71For hydrogen atom and X7、X8And X9Among 2 be dialkyl amido Compound, following compounds can be enumerated.
The compound for being 0 as the s in formula (7), it can be cited for example that bis- (dimethylamino) ethylene methacrylic base silanes, double (diethylamino) ethylene methacrylic base silane, bis- (dipropylamino) ethylene methacrylic base silanes, bis- (dibutylamino) methyl second Alkenyl silanes, bis- (dimethylamino) ethylethylene base silanes, bis- (diethylamino) ethylethylene base silanes, bis- (dipropyl Amino) ethylethylene base silane and bis- (dibutylamino) ethylethylene base silanes.
The compound for being 1 as the s in formula (7), it can be cited for example that bis- (dimethylamino) methyl (4- vinyl benzenes Base) silane, bis- (dimethylamino) methyl (3- ethenylphenyl) silane, bis- (diethylamino) methyl (4- ethenylphenyl) Silane, bis- (diethylamino) methyl (3- ethenylphenyl) silane, bis- (dipropylamino) methyl (4- ethenylphenyl) silicon Alkane, bis- (dipropylamino) methyl (3- ethenylphenyl) silane, bis- (dibutylamino) methyl (4- ethenylphenyl) silane, It is bis- (dibutylamino) methyl (3- ethenylphenyl) silane, bis- (dimethylamino) ethyls (4- ethenylphenyl) silane, double (dimethylamino) ethyl (3- ethenylphenyl) silane, bis- (diethylamino) ethyls (4- ethenylphenyl) silane, bis- (two Ethylamino) ethyl (3- ethenylphenyl) silane, bis- (dipropylamino) ethyls (4- ethenylphenyl) silane, bis- (dipropyls Base amino) ethyl (3- ethenylphenyl) silane, bis- (dibutylamino) ethyl (4- ethenylphenyl) silane and bis- (dibutyl Amino) ethyl (3- ethenylphenyl) silane.
Among formula (7) compound represented, as R71For methyl, X7、X8And X9Among 2 be dialkyl amido change Object is closed, following compounds can be enumerated.
The compound for being 1 as the s in formula (7), it can be cited for example that bis- (dimethylamino) methyl (4- isopropenylbenzenes Base) silane, bis- (dimethylamino) methyl (3- isopropenyl phenyl) silane, bis- (diethylamino) methyl (4- isopropenyls Phenyl) silane, bis- (diethylamino) methyl (3- isopropenyl phenyl) silane, bis- (dipropylamino) methyl (4- isopropyl alkene Base phenyl) silane, bis- (dipropylamino) methyl (3- isopropenyl phenyl) silane, bis- (dibutylamino) methyl (4- isopropyls Alkenyl phenyl) silane, bis- (dibutylamino) methyl (3- isopropenyl phenyl) silane, (4- is different for bis- (dimethylamino) ethyls Acrylic phenyl) silane, bis- (dimethylamino) ethyls (3- isopropenyl phenyl) silane, bis- (diethylamino) ethyl (4- Isopropenyl phenyl) silane, bis- (diethylamino) ethyls (3- isopropenyl phenyl) silane, bis- (dipropylamino) ethyls (4- isopropenyl phenyl) silane, bis- (dipropylamino) ethyls (3- isopropenyl phenyl) silane, bis- (dibutylamino) second Base (4- isopropenyl phenyl) silane and bis- (dibutylamino) ethyls (3- isopropenyl phenyl) silane.
As compound shown in formula (7), as R71For vinyl, X7、X8And X9Among 2 be dialkyl amido Compound, following compounds can be enumerated.
The compound for being 0 as the s in formula (7), it can be cited for example that bis- (dimethylamino) methyl (1- methylene -2- Acrylic) silane, bis- (diethylamino) methyl (1- methylene -2- acrylic) silane, bis- (dipropylamino) methyl (Asia 1- Methyl -2- acrylic) silane, bis- (dibutylamino) methyl (1- methylene -2- acrylic) silane, bis- (dimethylamino) second Base (1- methylene -2- acrylic) silane, bis- (diethylamino) ethyls (1- methylene -2- acrylic) silane, bis- (dipropyl Amino) ethyl (1- methylene -2- acrylic) silane and bis- (dibutylamino) ethyls (1- methylene -2- acrylic) silane.
As compound shown in formula (7), as R71For phenyl, X7、X8And X9Among 2 for dialkyl amido Compound can enumerate following compounds.
The compound for being 1 as the s in formula (7), it can be cited for example that 1- { 4- [bis- (dimethylamino) methyl silicanes Base] phenyl } -1- phenylethylene, 1- { 4- [bis- (diethylamino) methyl silicane bases] phenyl } -1- phenylethylene, 1- { 4- [bis- (dipropylamino) methyl silicane bases] phenyl } -1- phenylethylene, 1- { 4- [bis- (dibutylamino) methyl silicanes Base] phenyl } -1- phenylethylene, 1- { 4- [bis- (dimethylamino) ethyl silicane bases] phenyl } -1- phenylethylene, 1- { 4- [bis- (diethylamino) ethyl silicane bases] phenyl } -1- phenylethylene, 1- { 4- [bis- (dipropylamino) ethyl silicanes Base] phenyl } -1- phenylethylene and 1- { 4- [bis- (dibutylamino) ethyl silicane bases] phenyl } -1- phenylethylene.
As compound shown in formula (7), as R71For hydrogen atom, X7、X8And X9In 3 for dialkyl amido Compound can enumerate following compounds.
The compound for being 0 as the s in formula (7), it can be cited for example that three (dimethylamino) vinyl silanes, three (two Ethylamino) vinyl silanes and three (dipropylamino) vinyl silanes, three (dibutylamino) vinyl silanes.
The compound for being 1 as the s in formula (7), it can be cited for example that three (dimethylaminos) (4- ethenylphenyl) silicon Alkane, three (dimethylaminos) (3- ethenylphenyl) silane, three (diethylaminos) (4- ethenylphenyl) silane, three (diethyls Base amino) (3- ethenylphenyl) silane, three (dipropylaminos) (4- ethenylphenyl) silane, three (dipropylamino) (3- Ethenylphenyl) silane, three (dibutylaminos) (4- ethenylphenyl) silane and three (dibutylamino) (3- vinyl benzenes Base) silane.
As compound shown in formula (7), as R71For methyl, X7、X8And X9In 3 be dialkyl amido change Object is closed, following compounds can be enumerated.
The compound for being 1 as the s in formula (7), it can be cited for example that three (dimethylaminos) (4- isopropenyl phenyl) Silane, three (dimethylaminos) (3- isopropenyl phenyl) silane, three (diethylaminos) (4- isopropenyl phenyl) silane, three (diethylamino) (3- isopropenyl phenyl) silane, three (dipropylaminos) (4- isopropenyl phenyl) silane, three (dipropyl Amino) (3- isopropenyl phenyl) silane, three (dibutylaminos) (4- isopropenyl phenyl) silane and three (dibutylaminos) (3- isopropenyl phenyl) silane.
As compound shown in formula (7), as R71For vinyl, X7、X8And X9In 3 for dialkyl amido Compound can enumerate following compounds.
The compound for being 0 as the s in formula (7), it can be cited for example that three (dimethylaminos) (1- methylene -2- propylene Base) silane, three (diethylaminos) (1- methylene -2- acrylic) silane, three (dipropylaminos) (1- methylene -2- propylene Base) silane and three (dibutylaminos) (1- methylene -2- acrylic) silane.
As compound shown in formula (7), as R71For phenyl, X7、X8And X9Among 3 for dialkyl amido Compound can enumerate following compounds.
The compound for being 1 as the s in formula (7), it can be cited for example that 1- [4- tri- (dimethylamino) silicyl benzene Base] -1- phenylethylene, 1- [(diethylamino) silicyl of 4- tri- phenyl] -1- phenylethylene, the 1- [(two-n-propyls of 4- tri- Amino) methyl silicane base phenyl] -1- phenylethylene and 1- [(di-n-butyl amino) the methyl silicane base of 4- tri- phenyl] -1- Phenylethylene.
It is the X in formula (7) as preferred compound in group shown in formula (7)7、X8And X9Among 2 be dioxane X in the compound of base amino, more preferably formula (7)7、X8And X9Among 2 be dialkyl amido, R71For hydrogen atom, s 0 Compound.
As formula (7) compound represented, most preferably bis- (dimethylamino) ethylene methacrylic base silanes, bis- (diethyl Amino) ethylene methacrylic base silane, bis- (dipropylamino) ethylene methacrylic base silanes, bis- (dibutylamino) methyl ethylene silicon Alkane, bis- (dimethylamino) ethylethylene base silanes, bis- (diethylamino) ethylethylene base silanes, bis- (dipropylamino) second Base vinyl silanes, bis- (dibutylamino) ethylethylene base silanes.
Modifying agent may include the compound shown in following formula (8) containing nitrogen-atoms and carbonyl.
[changing 17]
。
In formula (8), R81And R82It each independently represents the alkyl optionally with substituent group or indicates R81In one Point and R82In a part bonding obtained from optionally with the alkylene of nitrogen-atoms and/or oxygen atom, R84Expression optionally has The alkyl or hydrogen atom or formation R of substituent group81And R82In a part and R in any one84In a part bonding and obtain The optionally alkylene with nitrogen-atoms and/or oxygen atom arrived.In addition, R83Indicate that divalent group, n are 0 or 1.
R81、R82And R84In optionally refer to alkyl or substituted alkyl with the alkyl of substituent group.As substituted hydrocarbon Base, it can be cited for example that the alkyl etc. replaced by alkyl that oxyl replaces, substituted amino.
As alkyl, it can be cited for example that alkyl, alkenyl, alkynyl, aryl and aralkyl.As alkyl, preferably carbon is former The alkyl that subnumber is 1 ~ 12, it can be cited for example that methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl, just Amyl, n-hexyl, n-octyl, dodecyl, cyclopenta and cyclohexyl.As alkenyl, preferably carbon atom number is 2 ~ 12 Alkenyl, it can be cited for example that vinyl, allyl, 1- acrylic and isopropenyl.As alkynyl, preferably carbon atom number be 2 ~ 12 alkynyl, it can be cited for example that acetenyl and 2-propynyl.As aryl, preferably carbon atom number is 6 ~ 12 aryl, can To enumerate such as phenyl, aminomethyl phenyl, ethylphenyl, benzyl, tolyl and xylyl.As aralkyl, preferably carbon The aralkyl that atomicity is 7 ~ 13, it can be cited for example that benzyl.
As the alkyl replaced by oxyl, it can be cited for example that methoxy, ethoxyl methyl, ethoxyethyl group etc. Alkoxyalkyl.
As the alkyl that substituted amino replaces, it can be cited for example that N, N- dimethylaminomethyl, 2- (N, N- diformazan Base amino) ethyl, 2- (N, N- diethylamino) ethyl, 3- (N, N- dimethylamino) propyl, 3- (N, N- diethylamino) Propyl etc. (N, N- dialkyl amido) alkyl；4- (N, N- dimethylamino) phenyl, 3- (N, N- dimethylamino) phenyl, 4- (N, the N- dialkyl amido) aryl such as (N, N- diethylamino) phenyl, 3- (N, N- diethylamino) phenyl；4- (N, N- diformazan Base amino) (N, the N- dialkyl amido) alkylaryl such as aminomethyl phenyl, 4- [2- (N, N- dimethylamino) ethyl] phenyl；3- The alkyl that (1- pyrrolidinyl) propyl, 3- (1- piperidyl) propyl, 3- (1- imidazole radicals) propyl etc. are replaced by cyclic amino；4- The aryl that (1- pyrrolidinyl) phenyl, 4- (1- piperidyl) phenyl, 4- (1- imidazole radicals) phenyl etc. are replaced by cyclic amino；4- [2- (1- pyrrolidinyl) ethyl] phenyl, 4- [2- (1- piperidyl) ethyl] phenyl, 4- [2- (1- imidazole radicals) ethyl] phenyl etc. The alkylaryl replaced by cyclic amino.
R81In a part and R82In a part bonding obtained from group or R81And R82In in any one one Part and R84In a part bonding obtained from group, the alkylene optionally with nitrogen-atoms and/or oxygen atom refers to Asia Alkyl or alkylene with nitrogen-atoms and/or oxygen atom.
As alkylene, it can be cited for example that trimethylene, tetramethylene, pentamethylene, hexa-methylene, 2,2,4- front threes The alkylidenes such as base hex- 1,6- diyl；The arlydene such as 1,4- phenylene.As the sub- hydrocarbon optionally with nitrogen-atoms and/or oxygen atom Base, it can be cited for example that group shown in-CH=N-CH=CH- ,-CH=N-CH2-CH2Shown in group ,-(CH2)t-O- (CH2)uShown in group (integer that t and u are 1 or more) etc..
As R83In divalent group, it can be cited for example that alkylene, the alkylene with nitrogen-atoms and/or oxygen atom, Asia Group obtained from alkyl and oxygen atoms bond or alkylene and-NR85Shown in group (R85Indicate alkyl or hydrogen atom) key Group obtained from conjunction.
As alkylene, it can be cited for example that alkylidene, alkene diyl, arlydene, arlydene and alkylidene be bonded and Obtained group (hereinafter sometimes referred to arylene-alkylene) etc..As alkylidene, it can be cited for example that methylene, ethylidene, Propylidene, tetramethylene, pentamethylene, hexa-methylene, heptamethylene, eight methylene and 2,2,4- trimethyl hex- 1,6- diyl. As alkene diyl, it can be cited for example that amyl- 2- alkene -1,5- diyl.As arlydene, it can be cited for example that phenylene, sub- naphthalene Base and biphenylene.As arylene-alkylene, it can be cited for example that phenylene-alkylidene, naphthylene-alkylidene and Ya Lian Phenyl-alkylidene.
As the alkylene with nitrogen-atoms nitrogen-atoms and/or oxygen atom, it can be cited for example that shown in-CH=N-CH=CH- Group ,-CH=N-CH2-CH2Shown in group ,-(CH2)t-O-(CH2)uShown in group (integer that t and u are 1 or more) Deng.As group obtained from alkylene and oxygen atoms bond, it can be cited for example that-(CH2)uGroup shown in-O- (u be 1 with On integer).
As alkylene and-NR85Shown in group (R85Indicate alkyl or hydrogen atom) group obtained from bonding, it can be with Enumerate such as-(CH2) (R indicates that carbon atom number is 1 or more and 10 alkyl or hydrogen atom below to group shown in v-NR-, and v is 1 or more integer) etc..
As compound shown in above-mentioned formula (8), preferably n is 0, R84Indicate alkyl or hydrogen optionally with substituent group The compound of atom, i.e. following formula (8-1) compound represented；N is 0, indicates R81In a part and R84In a part of key Alkylene or alkylene obtained from conjunction and-NR85Shown in group (R85Indicate alkyl or hydrogen atom) base obtained from bonding The compound of group, i.e. following formula (8-2) compound represented；N is 1, R83Indicate the compound of alkylene, i.e. following formula (8-3) Compound represented；Or n is 1, R83Indicate group obtained from alkylene and oxygen atoms bond or alkylene and-NR85It is shown Group (R85Indicate alkyl or hydrogen atom) compound of group obtained from bonding, i.e. following formula (8-4) compound represented.
[changing 18]
In formula (8-1), R81、R82And R84With the R in above-mentioned formula (8)81、R82And R84It is synonymous.
[changing 19]
In formula (8-2), R82With the R in above-mentioned formula (8)82It is synonymous.R86Indicate alkylene or alkylene and-NR85Shown in base Group (R obtained from group's bonding85Indicate alkyl or hydrogen atom).
[changing 20]
In formula (8-3), R81、R82And R84With the R in above-mentioned formula (8)81、R82And R84It is synonymous.R83Indicate alkylene.
[changing 21]
In formula (8-4), R81、R82And R84With the R in above-mentioned formula (8)81、R82And R84It is synonymous.R87Indicate that alkylene, A indicate that oxygen is former Son or-NR85-(R85Indicate alkyl or hydrogen atom).
As the R in formula (8-1)81And R82, preferably each independently representing carbon atom number is 1 or more and 10 hydrocarbon below Base or expression R81In a part and R82In a part bonding obtained from carbon atom number be 3 or more and 10 Asias below Alkyl or carbon atom number are 3 or more and 10 alkylene below with nitrogen-atoms, more preferably each independently indicate carbon atom Number is 1 or more and 10 alkyl below or carbon atom number is 6 or more and 10 aryl below or expression R81In a part With R82In a part bonding obtained from carbon atom number be 3 or more and 10 alkylidenes below, shown in-CH=N-CH=CH- Group or CH=N-CH2-CH2Shown in group, further preferably each independently represent carbon atom number be 1 or more and 6 or less Alkyl, still more preferably each independently represent methyl or ethyl.
As the R in formula (8-1)84, preferably expression alkyl or hydrogen atom, more preferable expression carbon atom number are 1 or more and 10 Alkyl or hydrogen atom below, further preferably indicate carbon atom number be 1 or more and 6 alkyl or hydrogen atom below, more into One step preferably indicates hydrogen atom, methyl or ethyl.
Among formula (8-1) compound represented, as R84The compound for indicating alkyl, it can be cited for example that N, N- dimethyl Acetamide, N, the N such as N- diethyl acetamide, N- methyl-N ethyl acetamide, N- dialkyl acetamide；N- dimethyl allene acyl Amine, N, the N such as N- acrylamide, N- methyl-N-ethylacrylamide, N- dialkyl acrylamide；N, N- dimethyl methyl Base acrylamide, N, the N such as N- diethyhnethacrylamide, N- methyl-N ethyl Methacrylamide, N- dialkyl methyl-prop Acrylamide.
Among formula (8-1) compound represented, as R84The compound for indicating hydrogen atom, it can be cited for example that N, N- diformazan Base formamide, N, the N such as N- diethylformamide, N- methyl-N-ethylcarboxamide, N- dialkyl formamide.
In formula (8-2), as R86In alkylene, it can be cited for example that alkylidene, alkene diyl, arlydene or arlydene With group obtained from alkylene (hereinafter sometimes referred to arylene-alkylene) etc..As alkylidene, preferably carbon atom Number be 1 ~ 12 alkylidene, it can be cited for example that methylene, ethylidene, propylidene, tetramethylene, pentamethylene, hexa-methylene, Heptamethylene, eight methylene, 2,2,4- trimethyl hex- 1,6- diyl etc..As alkene diyl, preferably carbon atom number is 4 ~ 12 Alkene diyl, it can be cited for example that amyl- 2- alkene -1,5- diyl etc., as arlydene, preferably carbon atom number be 6 ~ 12 Asia Aryl, it can be cited for example that phenylene, naphthylene, biphenylene etc..As arylene-alkylene, it can be cited for example that sub- benzene Base-alkylidene, naphthylene-alkylidene, biphenylene-alkylidene etc..As R86In alkylene and-NR85Shown in group (R85Indicate alkyl or hydrogen atom) group obtained from bonding, it can be cited for example that-(CH2)v(R is indicated group shown in-NR- Carbon atom number is 1 or more and 10 alkyl or hydrogen atom below, the integer that v is 1 or more) etc..
As the R in formula (8-2)82, preferably expression carbon atom number is 1 or more and 10 alkyl below, more preferably expression carbon Atomicity is 1 or more and 10 alkyl below or carbon atom number is 6 or more and 10 aryl below, further preferably expression carbon Atomicity is 1 or more and 6 alkyl or phenyls below, still more preferably expression methyl, ethyl or phenyl.
As the R in formula (8-2)86, preferably expression carbon atom number is 1 or more and 10 alkylene below or carbon atom number For 1 or more and 10 alkylene below and-NR88Shown in group (R88Expression carbon atom number is 1 or more and 10 alkyl below Or hydrogen atom) bonding obtained from group, more preferably indicate carbon atom number be 3 or more and 6 alkylidenes below or-(CH2)w- Group shown in NR- (R indicates that carbon atom number is 1 or more and 10 alkyl below, and w is 2 or more and 5 integers below), into one Step is preferred to indicate trimethylene, tetramethylene, pentamethylene or-(CH2)2-N(CH3)-shown in group.
Among formula (8-2) compound represented, as R86The compound for indicating alkylene, it can be cited for example that N- methyl- N- alkyl-the azetidinones such as azetidinone, N- phenyl-azetidinone；N-methyl-2-pyrrolidone, N- vinyl -2- The N- hydrocarbon such as pyrrolidones, N-Phenyl-2-Pyrrolidone, N- tert-butyl -2-Pyrrolidone, N- methyl -5- N-methyl-2-2-pyrrolidone N Base -2-Pyrrolidone；N- alkyl -2- the piperazines such as N- methyl -2- piperidones, N- vinyl -2- piperidones, N- phenyl -2- piperidones Pyridine ketone；N- alkyl-the epsilon-caprolactams such as N- methyl-E-caprolactam, N- phenyl-epsilon-caprolactams；In N- methyl-ω-ten two N- alkyl-the omega-lauric lactams such as amide, N- vinyl-omega-lauric lactam.Among these, preferably N- methyl -2- pyrrole Pyrrolidone, N-Phenyl-2-Pyrrolidone, N- methyl-E-caprolactam, N- phenyl-epsilon-caprolactams, further preferably N- benzene Base -2-Pyrrolidone, N- methyl-E-caprolactam.
Among formula (8-2) compound represented, as R86Indicate alkylene and-NR85Shown in group (R85For alkyl or Hydrogen atom) bonding obtained from group compound, it can be cited for example that 1,3- dimethyl -2- imidazolidinone, 1,3- diethyl - 1,3- dialkyl -2- the miaows such as 2- imidazolidinone, 1,3- divinyl -2- imidazolidinone, 1- methyl -3- ethyl -2- imidazolidinone Oxazolidone.Among these, preferably 1,3- dimethyl -2- imidazolidinone, 1,3- diethyl -2- imidazolidinone, further preferably For 1,3- dimethyl -2- imidazolidinone.
As the R in formula (8-3)83, preferably expression carbon atom number is 1 or more and 10 alkylene below, is more preferably indicated Carbon atom number is 1 or more and 10 alkylidenes below or carbon atom number is 6 or more and 10 arlydene below, further preferably Expression carbon atom number be 1 or more and 6 alkylidenes or phenylene below, still more preferably expression ethylidene, trimethylene or 1,4- phenylene.
As the R in formula (8-3)84, preferably expression carbon atom number is for 1 or more and 10 alkyl below or by dialkyl amino The carbon atom number that base replaces is 3 or more and 10 alkyl below, more preferably indicate carbon atom number be 1 or more and 6 alkyl below, Carbon atom number is 6 or more and 10 aryl below, carbon atom number is 3 or more and 6 dialkyl aminoalkyls or carbon atom below Number is 8 or more and 10 dialkylaminoaryls below, and further preferably expression methyl, ethyl, carbon atom number are 3 or more and 6 Dialkylaminomethyl group below, carbon atom number are that 4 or more and 6 di-alkyaminoethyl group, phenyl or carbon atom numbers below are 8 or more and 10 dialkylaminophenyls below.
As the R in formula (8-3)81And R82, preferably each independently representing carbon atom number is 1 or more and 10 hydrocarbon below Base or expression R81In a part and R82In a part bonding obtained from carbon atom number be 3 or more and 10 Asias below Alkyl or carbon atom number are 3 or more and 10 alkylene below with nitrogen-atoms, more preferably each independently indicate carbon atom Number is 1 or more and 10 alkyl below or carbon atom number is 6 or more and 10 aryl below or expression R81With R82、R81With R82Group obtained from bonding indicates that carbon atom number is 3 or more and 10 alkylidenes below, base shown in-CH=N-CH=CH- Group ,-CH=N-CH2-CH2Shown in group or-(CH2)2-O-(CH2)2Shown in group, further preferably each independently Indicate that carbon atom number is 1 or more and 6 alkyl below or expression R81In a part and R82In a part bonding and obtain The carbon atom number arrived is 3 or more and 6 alkylidenes below, group or-CH=N-CH shown in-CH=N-CH=CH-2-CH2It is shown Group, still more preferably each independently represent methyl or ethyl or indicate R81In a part and R82In one Divide group shown in tetramethylene, hexa-methylene or-CH=N-CH=CH- obtained from bonding.
Among formula (8-3) compound represented, as R83Indicate arlydene, R84The compound for indicating alkyl, can enumerate Such as 4- (N, N- dimethylamino) acetophenone, 4- (N- methyl-N-ethylamino) acetophenone, 4- (N, N- diethylamino) benzene The 4- such as ethyl ketone (N, N- Dialkylamino) acetophenone；The 4- cyclic amino acetophenone compounds such as 4'- (imidazoles -1- base) acetophenone. Among these, preferably 4- cyclic amino acetophenone compound, more preferably 4'- (imidazoles -1- base) acetophenone.
Among formula (8-3) compound represented, as R83Indicate alkylene, R84Indicate the change of alkyl or substituted alkyl Object is closed, it can be cited for example that 1,7- bis- (methylethylamine) -4- heptanone, bis- (diphenyl amino) -2- acetone of 1,3- etc. bis- (two Hydrocarbylamino alkyl) ketone.As R83Indicate arlydene, R84The compound for indicating aryl or substituted aryl, it can be cited for example that 4- N, N- dimethylamino benzophenone, 4-N, N- diethylamino benzophenone, 4-N, N- di-t-butyl aminobenzophenone, 4-N, N- diphenyl amino benzophenone etc. 4- (Dialkylamino) benzophenone；Bis- (dimethylamino) benzophenone of 4,4'-, The 4,4'- bis- (Dialkylaminos) such as bis- (diethylamino) benzophenone of 4,4'-, bis- (diphenyl amino) benzophenone of 4,4'- Benzophenone.Among these, bis- (the methylethylamine) -4- heptanone of preferably 1,7-, 4-N, N- dimethylamino benzophenone, Bis- (dimethylamino) benzophenone of 4-N, N- diethylamino benzophenone, 4,4'-, bis- (diethylamino) hexichol of 4,4'- Ketone, more preferably 4-N, N- dimethylamino benzophenone, 4-N, N- diethylamino benzophenone, the bis- (dimethyl of 4,4'- Amino) benzophenone, bis- (diethylamino) benzophenone of 4,4'-.
In formula (8-4), as the oxygen atom or-NR in A85-(R85Indicate alkyl or hydrogen atom), preferably expression oxygen atom, Or group shown in-NR- (R indicates that carbon atom number is 1 or more and 5 alkylene or hydrogen atom below), more preferably indicate that oxygen is former Group shown in son or-NH-, group shown in further preferred expression-NH-.
In formula (8-4), as R87In alkylene, it can be cited for example that alkylidene, alkene diyl, arlydene, arlydene With alkylidene be bonded obtained from group (hereinafter sometimes referred to arylene-alkylene) etc..As alkylidene, preferably carbon is former The alkylidene that subnumber is 1 ~ 12, it can be cited for example that methylene, ethylidene, propylidene, tetramethylene, pentamethylene, six methylenes Base, heptamethylene, eight methylene, 2,2,4- trimethyl hex- 1,6- diyl etc..As alkene diyl, preferably carbon atom number is 4 ~ 12 alkene diyl, it can be cited for example that amyl- 2- alkene -1,5- diyl etc..As arlydene, preferably carbon atom number is 6 ~ 12 Arlydene, it can be cited for example that phenylene, naphthylene, biphenylene etc..As arylene-alkylene, it can be cited for example that Phenylene-alkylidene, naphthylene-alkylidene, biphenylene-alkylidene etc..
As the R in formula (8-4)84, preferably expression carbon atom number is 1 or more and 10 alkyl below, more preferably expression carbon Atomicity is 2 or more and 5 alkenyls below, further preferably indicates vinyl or isopropenyl, still more preferably expression second Alkenyl.
As the R in formula (8-4)87, preferably expression carbon atom number is 1 or more and 10 alkylene below, is more preferably indicated Carbon atom number is 1 or more and 6 alkylidenes below, further preferably indicates ethylidene or trimethylene, still more preferably table Show trimethylene.
As the R in formula (8-4)81And R82, preferably each independently representing carbon atom number is 1 or more and 10 hydrocarbon below Base or expression R81In a part and R82In a part bonding obtained from carbon atom number be 3 or more and 10 Asias below Alkyl or carbon atom number are 3 or more and 10 alkylene below with nitrogen-atoms, more preferably each independently indicate carbon atom Number is 1 or more and 10 alkyl below or carbon atom number is 6 or more and 10 aryl below or expression R81In a part With R82In a part bonding obtained from carbon atom number be 3 or more and 10 alkylidenes below, shown in-CH=N-CH=CH- Group ,-CH=N-CH2-CH2Shown in group or-(CH2)2-O-(CH2)2Shown in group, it is further preferably respectively independent Ground indicates that carbon atom number is 1 or more and 6 alkyl below or expression R81In a part and R82In a part bonding and Obtained carbon atom number is 3 or more and 6 alkylidenes below, group or-CH=N-CH shown in-CH=N-CH=CH-2-CH2Institute The group shown still more preferably each independently represents methyl or ethyl or indicates R81In a part and R82In Group shown in tetramethylene, hexa-methylene or-CH=N-CH=CH- obtained from a part bonding.
Among formula (8-4) compound represented, the compound of oxygen atom is indicated as A, it can be cited for example that acrylic acid 2- Acrylic acid 2- (Dialkylamino) ethyl esters such as (dimethylamino) ethyl ester, acrylic acid 2- (diethylamino) ethyl ester；Acrylic acid 3- (dimethylamino) propyl ester etc. acrylic acid 3- (Dialkylamino) propyl ester；Methacrylic acid 2- (dimethylamino) ethyl ester, methyl Acrylic acid 2- (diethylamino) ethyl ester etc. methacrylic acids 2- (Dialkylamino) ethyl ester；Methacrylic acid 3- (dimethylamino Base) methacrylic acids 3- (Dialkylamino) propyl ester such as propyl ester.Among these, preferably acrylic acid 2- (dimethylamino) second Ester, acrylic acid 3- (dimethylamino) propyl ester, methacrylic acid 2- (dimethylamino) ethyl ester, methacrylic acid 3- (dimethyl Amino) propyl ester, more preferably acrylic acid 2- (dimethylamino) ethyl ester, acrylic acid 3- (dimethylamino) propyl ester.
Among formula (8-4) compound represented, as A expression-NR85-(R85Indicate alkylene or hydrogen atom) shown in base The compound of group, it can be cited for example that N- (2- dimethyl aminoethyl) acrylamide, N- (2- diethylamino ethyl) propylene The N- such as amide (2- Dialkylamino ethyl) acrylamide；N- (3- dimethylaminopropyl) acrylamide, N- (3- diethyl amino Base propyl) N- (the 3- Dialkylamino propyl) acrylamide such as acrylamide；N- (4- dimethrlaminobutyl) acrylamide, N- (4- diethylamino butyl) acrylamide etc. N- (4- Dialkylamino butyl) acrylamide；N- (2- dimethyl aminoethyl) N- (the 2- Dialkylamino ethyl) methacryls such as Methacrylamide, N- (2- diethylamino ethyl) Methacrylamide Amine；N- (the 3- bis- such as N- (3- dimethylaminopropyl) Methacrylamide, N- (3- diethyl amino propyl) Methacrylamide Hydrocarbylamino propyl) Methacrylamide；N- (4- dimethrlaminobutyl) Methacrylamide, N- (4- diethylamino fourth Base) N- (the 4- Dialkylamino butyl) Methacrylamide such as Methacrylamide.Among these, preferably N- (2- dimethyl Amino-ethyl) acrylamide, N- (3- dimethylaminopropyl) acrylamide, N- (4- dimethrlaminobutyl) acrylamide, More preferably N- (2- dimethyl aminoethyl) acrylamide, N- (3- dimethylaminopropyl) acrylamide.
(organo-metallic compound)
It, can be with as the compound of the organic metal with the unit process possessed by conjugated diene polymer based on modifying agent Use such as organic alkali metal compound, organic alkaline earth metal compound, organic amphiprotic metallic compound.These organometallics Two or more can be applied in combination by closing object, in addition, can add as needed to improve the reactivity of organo-metallic compound Above-mentioned regulator.
As the compound of organic alkali metal, can be used selected from the compound illustrated as above-mentioned polymerization initiator In compound.As the compound of organic alkali metal, it can be cited for example that organo-lithium compound, organosiloxane compound, organic Potassium compound and organocesium compounds.As the compound of organic alkali metal, preferably organo-lithium compound, more preferably have Carbon atom number be 1 or more and 20 alkyl below lithium compound, further preferably have carbon atom number be 1 or more and 10 with Under alkyl lithium compound, particularly preferably n-BuLi, s-butyl lithium or tert-butyl lithium.
As the compound of organic alkaline-earth metal, organo-magnesium compound, organocalcium compound, organic strontium chemical combination can be enumerated Object etc..As the compound of organic alkaline-earth metal, preferably organo-magnesium compound, more preferably have carbon atom be 1 or more and The magnesium compound of 20 alkyl below is further preferably the magnesium chemical combination of 1 or more and 10 alkyl below with carbon atom number Object.As the compound of organic alkaline-earth metal, it can be cited for example that methyl-magnesium-chloride, methyl-magnesium-bromide, ethylmagnesium chloride, ethyl Magnesium bromide, n-propyl magnesium chloride, n-propyl magnesium bromide, isopropylmagnesium chloride, isopropyl magnesium bromide, n-butylmagnesium chloride magnesium, positive fourth Base magnesium bromide, sec-butyl magnesium chloride, sec-butyl magnesium bromide, tert-butyl magnesium chloride, tert-butyl magnesium bromide, allylmgcl, alkene Propyl magnesium bromide, vinyl magnesium bromide, phenyl-magnesium-chloride, phenyl-magnesium-bromide, benzyimag iesium chloride magnesium and benzyl magnesium bromide.
As the compound of organic amphiprotic metal, organic zinc compound, organo-aluminum compound etc. can be enumerated.As organic The compound of amphoteric metal, it is however preferred to have carbon atom is the organic zinc compound or organo-aluminium of 1 or more and 20 alkyl below Compound.As the compound of organic zinc, it can be cited for example that methyl chloride zinc, propyl zinc bromide, isopropylmagnesium bromide zinc, butyl The alkyl halogenation such as zinc bromide, sec-butyl zinc bromide, tert-butyl zinc bromide zinc compound, zinc methide, diethyl zinc, dibutyl The dialkyl zincs compounds such as zinc, diisopropyl zinc.As the compound of organo-aluminium, it can be cited for example that trimethyl aluminium, triethyl group Aluminium, triisobutyl aluminium, tri-n-hexyl aluminum, diethyl aluminum chloride, ethyl aluminium sesquichloride, ethylaluminum dichloride, isobutyl group dichloro Change aluminium, methylaluminoxane etc..
The additive amount of organo-metallic compound is not particularly limited, relative to modifying agent 1mol, preferably 0.1 ~ 10mol, More preferably 0.25 ~ 5.0mol, further preferably 0.5 ~ 2.0mol, particularly preferably 0.7 ~ 1.8mol.Thereby, it is possible to obtain The superior polymer composition of storage stability.
Organo-metallic compound as described above may be used as abovementioned steps 3, the Organometallic compounds in 3', 3'' and 1'' Object.
(coupling agent)
In the manufacturing method of modified conjugated diene polymer involved in present embodiment, to rear from the polymerization of monomer Until the recycling for the polymer stated, coupling agent can be added into polymeric solution.As coupling agent, above-mentioned formula (5) can be enumerated Or (6) compound represented.
The additive amount of coupling agent is not particularly limited, and when polymerization initiator includes alkali metal, is generated to be easy to be kneaded Modified conjugated diene polymer, relative to alkali metal 1mol, preferably 0.03mol or more, more preferably 0.05mol or more. In addition, the additive amount of coupling agent is to improve province's burnup of modified conjugated diene polymer composition, relative to alkali metal 1mol, preferably 0.4mol or less, more preferably 0.3mol or less.
(manufacture of modified conjugated diene polymer)
It is further described below for the embodiment of the manufacture of modified conjugated diene polymer of the invention.
As one of embodiment, the method (the 1st embodiment) comprising following step 1 ~ 3 is enumerated.
Step 1: making the monomer comprising conjugated diene compound in the presence of polymerization initiator, to obtain active The polymer 1 of end.
Step 2: making aforementioned modifiers and polymer 1 with the functional group that can be reacted with the reactive terminal of polymer 1 Reaction, to obtain having imported the polymer 2 of the unit based on aforementioned modifiers in the end of polymer 1.
Step 3: adding organo-metallic compound to polymer 2, make unit and organometallic based on aforementioned modifiers Object reaction is closed, modified conjugated diene polymer according to the present invention is thus obtained.
Polymerization methods in step 1 are not particularly limited, and can be carried out with intermittent (batch-type) or continous way.As anti- Device is answered, batch reactor or tube-type reactor with blender can be used.In continuous polymerization methods, it can be used connected 2 or more reactors, continuous tank reactor also can be used.
Step 2 the reactive terminal of polymer 1 there are in the state of implement.
As modifying agent used in step 2, the preferably aforementioned compound with structure shown in formula (5) has formula (6) compound of structure shown in and the compound with structure shown in formula (8).
Step 2, can be and the addition modifying agent into the reactor of implementation steps 1 when with intermittent implementation steps 1 Implement, it can also be by the way that polymer 1 be transferred to another reactor, simultaneously under conditions of the reactive terminal of polymer 1 does not disappear Modifying agent is contacted with polymer 1 in another reactor and is implemented.In addition, step 2 is when with continous way implementation steps 1, It can implement and waning to the close and add modifying agent into reactor by polymerization reaction, use 2 s' or more to be connected It, can be by adding modifying agent into the 2nd reactor that is later and not putting into polymerization initiator when reactor carrys out implementation steps 1 And implement.
Step 3, can be by adding organic metal into the reactor of implementation steps 2 when with intermittent implementation steps 1 Compound and implement, by the way that polymer 2 is transferred to another reactor and organic metal can also be made in another reactor Compound contacts with polymer 2 and is implemented.In addition, step 3 is when with continous way implementation steps 1, it can be by than implementing to walk Rapid 2 more after part add organo-metallic compound into reactor and implement, step 3 is come using 2 connected reactors When implementation steps 1, it can be imported in other reactor and into the other reactor by taking out resulting polymers 2 Addition organo-metallic compound and implement, using 3 or more connected reactors and when implementation steps 1, can pass through to Than implementation steps 2 more after reactor in add organo-metallic compound and implement.
2nd embodiment of the manufacture as modified conjugated diene polymer of the invention, can enumerate comprising following Step 1' and step 3' method.
Step 1': make the monomer polymerization comprising conjugated diene compound in the presence of polymerization initiator.At this point, making to have It can polymerize together with the aforementioned modifiers for the functional group that conjugated diene compound is copolymerized, obtain polymer 1'.
Step 3': organo-metallic compound is added to polymer 1', makes unit and organic metal based on aforementioned modifiers Compound reaction, thus obtains modified conjugated diene polymer according to the present invention.
Polymerization methods in step 1' are not particularly limited, and can be carried out with intermittent (batch-type) or continous way.As Batch reactor or tube-type reactor with blender can be used in reactor.In continuous polymerization methods, phase can be used 2 or more reactors even, also can be used continuous tank reactor.
As modifying agent used in step 1', the preferably aforementioned compound with structure shown in formula (7).
Step 3', can be by adding organic gold into the reactor of implementation steps 1' when with intermittent implementation steps 1' Belong to compound and implement, can also be added with by the way that polymer 1' is transferred to another reactor and into another reactor Machine metallic compound and implement.In addition, step 3' when with continous way implementation steps 1', can pass through approaching in polymerization reaction End is added organo-metallic compound into reactor and is implemented, and is carrying out implementation steps using 2 or more connected reactors When 1', organo-metallic compound is added into the 2nd reactor that is later and not putting into aforementioned modifiers and is implemented.
It should be noted that, by implementing following step 2', can obtain polymerizeing after implementation steps 1' and before implementation steps 3' In the strand of object and end has the conjugated diene copolymer (polymer 2') of the unit based on modifying agent.
Step 2': make aforementioned modifiers and polymer with the functional group that can be reacted with the reactive terminal of polymer 1' 1' reaction, to obtain having imported the polymer 2' of the unit based on aforementioned modifiers in the end of polymer 1'.
As modifying agent used in step 2', the preferably aforementioned compound with structure shown in formula (5) has formula (6) compound of structure shown in and the compound with structure shown in formula (8).
It substitutes polymer 1' and uses polymer 2', to polymer 2' implementation steps 3', thus, it is possible to be obtained and polymer The corresponding modified conjugated diene polymer of 2'.The implementation of step 2' can be carried out according to step 2.In addition, implementation steps 2' In the case where the implementation of step 3' can also implement according to step 3.
3rd embodiment of the manufacture as modified conjugated diene polymer of the invention, can enumerate comprising following Step 1'' and step 3'' method.
Step 1'': make the monomer polymerization comprising conjugated diene compound in the presence of polymerization initiator.At this point, making to have The conjugation two that has the functional group that can be converted into the position that can be reacted with modifying agent and can be copolymerized with conjugated diene compound Ene compound and/or aromatic vinyl compound polymerize together, obtain polymer 1''-1.Thereafter, polymer 1''-1 institute is carried out The functional group having obtains polymer 1''-2 to the conversion at the position that can be reacted with modifying agent, make have can be with this The modifying agent and polymer 1''-2 of the functional group of functional group reactions after conversion react, and thus obtain polymer 1''.
Step 3'': adding organo-metallic compound to polymer 1'', makes unit and organic gold based on aforementioned modifiers Belong to compound reaction, thus obtains modified conjugated diene polymer according to the present invention.
The polymerization methods for obtaining polymer 1''-1 in step 1'' are not particularly limited, can be with intermittent (batch-type) Or continous way carries out.As reactor, batch reactor or tube-type reactor with blender can be used.Continuous polymerization In mode, 2 or more connected reactors can be used, continuous tank reactor also can be used.
As used in step 1'' have can be converted into modifying agent functional group and can be with conjugated diene compound The compound of the conjugated diene of copolymerization, can enumerate aforementioned conjugated diene compound, on side chain with double bond conjugated diene Compound etc..As used in step 1'' have can be converted into modifying agent functional group and can be with conjugated diene chemical combination The compound of the aromatic vinyl of object copolymerization, can enumerate vinyltoluene (2-methyl styrene, 3- methyl styrene, 4- first Base styrene) etc..Using polymer 1''-1 obtained from these compounds and with identical organic gold used in step 3'' Belong to compound reaction, be thus divested for example originating from the hydrogen of the allyl position of the double bond of conjugated diene compound, or is originated from virtue The hydrogen of the benzyl position of the aromatic rings of race's vinyl compound is divested, can be with so as to provide in polymer 1''-1 The position of modifying agent reaction, can obtain polymer 1''-2.
It is preferably aforementioned that there is formula (5) institute as the modifying agent reacted with the polymer 1''-2 obtained in this way The compound for the structure shown, the compound with structure shown in formula (6) and the compound with structure shown in formula (8).
With when obtaining the polymerization of polymer 1''-1, obtained in intermittent implementation steps 1'' polymer 1''-2 reaction, It can be added in the reactor by the polymerization for obtaining polymer 1''-1 to implementation with polymer 1''-2 with reacting for modifying agent Organo-metallic compound or modifying agent and implement respectively, can also be by the way that polymer 1''-1 or polymer 1''-2 be transferred to separately One reactor simultaneously adds organo-metallic compound or modifying agent into another reactor and implements respectively.In addition, being polymerize The reaction of object 1''-2 in continous way implementation steps 1'' in the case where obtaining the polymerization of polymer 1''-1, can pass through Organo-metallic compound is added into reactor and implement, using 2 or more to be connected in waning to the close for polymerization reaction It, can be by not putting into after the 2nd and the anti-of monomer in the case where polymerization of the reactor to implement to obtain polymer 1''-1 It answers in device and adds organo-metallic compound and implement.Polymer 1''-2 is reacted with modifying agent with continous way implementation steps 1'' In obtain the polymerization of polymer 1''-1 in the case where, can pass through than obtain polymer 1''-2 reaction more after part Modifying agent is added into reactor and is implemented, and comes in implementation steps 1'' to obtain polymer using 2 connected reactors In the case where the polymerization of 1''-1, it can be imported in other reactor and to this separately by taking out resulting polymers 1''-2 Modifying agent is added in outer reactor and is implemented, it can be into the reactor after the reaction more than obtain polymer 1''-2 It adds modifying agent and implements.
Step 3'' is in intermittent implementation steps 1'' in the case where obtaining the polymerization of polymer 1''-1, Ke Yitong It crosses and adds organo-metallic compound into the reactor for the reaction for implementing to obtain polymer 1'' and implement, it can also be by that will gather Object 1'' is closed to be transferred to another reactor and add organo-metallic compound into another reactor and implement.In addition, step 3'', can be by than being gathered in continous way implementation steps 1'' in the case where obtaining the polymerization of polymer 1''-1 Part after closing the reaction more of object 1'' is added organo-metallic compound into reactor and is implemented, and 2 or more to be connected are being used Polymerization of the reactor to implement to obtain polymer 1''-1 in the case where, can be imported separately by taking out resulting polymers 1'' In outer reactor and organo-metallic compound is added into the other reactor and is implemented, it can be to than gathered It adds organo-metallic compound in reactor after closing the reaction more of object 1'' and implements.
It should be noted that in implementation steps 1'' obtain polymer 1''-2 reaction after and implementation steps 3'' before, pass through implementation Following step 2'', can obtain in the strand of polymer and end has the conjugated diene of the unit based on modifying agent total Polymers (polymer 2'').
Step 2'': make aforementioned modifiers and polymerization with the functional group that can be reacted with polymer 1''-2 reactive terminal Object 1''-2 reaction, to obtain having imported the polymer 2'' of the unit based on aforementioned modifiers in the end polymer 1''-2.
As modifying agent used in step 2'', the preferably aforementioned compound with structure shown in formula (5) has The compound of structure shown in formula (6) and the compound with structure shown in formula (8).
It substitutes polymer 1'' and uses polymer 2'', to polymer 2'' implementation steps 3'', thus, it is possible to obtain and gather Close the corresponding modified conjugated diene polymer of object 2''.The implementation of step 2'' can be carried out according to step 2.In addition, implementing The implementation of step 3'' in the case where step 2'' can also be implemented according to step 3.
As the method for recycling modified conjugated diene polymer from the solution that polymer dissolves, can be used well known Method.As recovery method, it can be cited for example that adding coagulator into the solution containing modified conjugated diene polymer Method；Steam is blown into the solution containing modified conjugated diene polymer to make volatile ingredient gasify and (the vapour of removal Mention) method；With flash tank concentration, further with the method for the devolatilizations such as vacuum-extruder；It is directly taken off with roller drier etc. The method of volatilization.The modified conjugated diene polymer of recycling can be done well known to band drier, extrusion type drying machine etc. Dry machine and dry.In terms of processability, if with the application of the invention, if be easy to get the low polymer of Mooney viscosity, therefore preferably To utilize following recovery methods: with flash tank concentration, further with the method for the devolatilizations such as vacuum-extruder；It is done with roller The method of the directly devolatilization such as dry machine.In addition, if with the application of the invention, being then characterized in that also obtaining that Mooney viscosity is low, processability Excellent copolymer, in the case where application gas stripping process, the present invention is useful.
In the present invention, in order to improve the processability of modified conjugated diene polymer, before separating solvent, as needed may be used To mix extending oil into solution, modified conjugated diene polymer can be recycled as oil-extended rubber.
Mooney viscosity (the ML of modified conjugated diene polymer involved in present embodiment1+4) break to improve to stretch Resistance to spalling, preferably 10 or more, more preferably 20 or more.In addition, the Mooney viscosity of modified conjugated diene polymer is in order to mention High working property, preferably 200 or less, more preferably 150 or less.Mooney viscosity (ML1+4) according to JIS K6300 (1994) 100 It is measured at DEG C.
The vinyl bonds resultant of modified conjugated diene polymer involved in present embodiment is to be originated from conjugated diene Preferably 80mol% or less, the content for closing the monomeric unit of object is more preferably as 100mol% in order to improve province's burnup 70mol% or less.In addition, the vinyl bonds resultant of modified conjugated diene polymer is conjugated two in order to improve adherence properties, to be originated from The content of the monomeric unit of ene compound is as 100mol%, preferably 10mol% or more, more preferably 15mol% or more, into one Step is preferably 20mol% or more, particularly preferably 30mol% or more.The vinyl bonds resultant is by infrared spectrographic method, by second The absorption peak 910cm of alkenyl-1Neighbouring absorption intensity and find out.
Modified conjugated diene polymer involved in present embodiment has unit and organic metal based on modifying agent Structure obtained from compound reaction.Conjugated diene polymer is with from the above-mentioned modification with structure shown in formula (6) When the unit of agent, modified conjugated diene polymer can have structure shown in following formula (A1), (A2) or (A3).It is modified total Yoke diene polymer can for for example with structure shown in following formula (A1) polymer, have following formula (A2) shown in The mixture of the polymer of structure and the polymer with structure shown in following formula (A3).
[changing 22]
In formula (A1), (A2) and (A3), X2、X3、R61、R62, a and A1With synonymous, R those of in above-mentioned formula (6)91And R92Respectively It is 1 or more and 20 alkyl below from independently expression carbon atom number.R91And R92Preferably carbon atom number be 1 or more and 10 with Under alkyl.
Modified conjugated diene polymer involved in present embodiment can be for for example with knot shown in following formula (B) The polymer of structure.
[changing 23]
In formula (B), X3、R61、R62, a and A1With synonymous, R those of in above-mentioned formula (6)91Indicate carbon atom number be 1 or more and 20 alkyl below, n1 and k1 each independently represent the real number for meeting n1+k1=2.R91Preferably carbon atom number be 1 or more and 10 alkyl below.
Modified conjugated diene polymer involved in present embodiment can be for by making using shown in formula (7) The polymer of structure obtained from the conjugated diene copolymer that compound is modified is reacted with organo-metallic compound.
[manufacturing method of polymer composition]
Supporting material can be cooperated into modified conjugated diene polymer involved in present embodiment and prepare polymer group Close object.The manufacturing method of the polymer composition of present embodiment is included to above-mentioned 100 mass of modified conjugated diene copolymer Part is kneaded the step of supporting material of 10 ~ 150 mass parts.
As supporting material, it can be cited for example that silica, calcium silicates, alumina silicate and carbon black.They, which can be combined, makes Use two or more.
As silica, dry type silica (silicic acid anhydride), wet silicon dioxide (aqueous silicic acid), glue can be enumerated Body silica, precipitated silica etc..The BET specific surface area of silica is preferably 50m2/g~250m2/g.The BET compares table Area is measured according to ASTM D1993-03.As commercially available product, trade name " the ウ Le ト ラ of デ グ ッ サ corporation can be used シ Le VN3-G ", the trade name " VN3 " of Dong ソ ー シ リ カ corporation, " AQ ", " ER ", " RS-150 ", Rhodia corporation Trade name " Zeosil 1115MP ", " Zeosil 1165MP " etc..
As carbon black, black furnace black, acetylene black, hot tearing, channel black, graphite etc. can be enumerated.As carbon black, may be exemplified Channel black as EPC, MPC and CC out；SAF, ISAF, HAF, MAF, FEF, SRF, GPF, APF, FF, CF, SCF and ECF that The furnace black of sample；Thermal black as FT and MT；Acetylene carbon black.
Nitrogen adsorption specific surface area (the N of carbon black2It SA) is preferably 5m2/g~200m2/ g, in addition, the phthalic acid of carbon black Dibutyl ester (DBP) uptake is preferably 5mL/100g ~ 300mL/100g.The nitrogen adsorption specific surface area is according to ASTM D4820- 93 and measure, which measures according to ASTM D2414-93.As commercially available product, Mitsubishi Chemical Ind's system can be used Trade name " ダ イ ヤ Block ラ ッ Network N339 ", East Sea カ ー ボ Application corporation trade name " シ ー ス ト 6 ", " シ ー ス ト 7HM, " シ ー ス ト KH ", the trade name " CK 3 " of デ グ ッ サ corporation, " Special Black 4A " etc..
The content of supporting material in polymer composition is relative to 100 mass parts of modified conjugated diene polymer Raising abrasion performance and intensity are 10 mass parts or more, more than preferably 20 mass parts, more than more preferably 30 mass parts. It is 150 below the mass, preferably 120 below the mass, more preferably in addition, the content of supporting material is reinforcing in order to improve Below the mass for 100.
In modified conjugated diene polymer involved in present embodiment, can further cooperate other polymers at Point, additive etc. and prepare polymer composition.
As other polymers ingredient, styrene-butadiene copolymer rubber, polybutadiene rubber, fourth two can be enumerated Alkene-isoprene copolymer rubber, butyl rubber.Further, it is also possible to enumerate natural rubber, ethylene-propylene copolymer, ethylene- Octene copolymer etc..Two or more can be applied in combination in these component of polymer.
When cooperating other polymers ingredient, modified conjugated diene involved in the present embodiment in polymer composition The content of polymer is in order to improve burnup performance, and the total amount relative to the component of polymer in polymer composition is (comprising being modified Conjugated diene polymer) 100 mass %, preferably 10 mass % or more, more preferably 20 mass % or more.
As additive, well known additive can be used, the vulcanizing agents such as sulphur can be enumerated；Thiazole system vulcanization accelerator, The vulcanization accelerators such as thiuram system vulcanization, sulfenamide system vulcanization accelerator, guanidine system vulcanization accelerator；Stearic acid, oxygen Change the vulcanizing activators such as zinc；The organic peroxides such as cumyl peroxide, di-tert-butyl peroxide；Calcium carbonate, talcum, oxygen Change the fillers such as aluminium, clay, aluminium hydroxide, mica；Silane coupling agent；Extending oil；Processing aid；Anti-aging agent；Lubricant.
As sulphur, powder sulphur, precipitated sulfur, colloid sulphur, insoluble sulfur, polymolecularity sulphur can be enumerated.The use level phase of sulphur It is preferably 0.1 ~ 15 mass parts for 100 mass parts of component of polymer, more preferably 0.3 ~ 10 mass parts, is more preferably 0.5 ~ 5 mass parts.
As vulcanization accelerator, 2-mercaptobenzothiazole, bisbenzothiazole disulphide, N- cyclohexyl -2- can be enumerated The thiazole systems vulcanization accelerator such as benzothiazole sulfenamide；Tetra methylthiuram list sulfide, tetramethyl thiuram disulfide Etc. thiuram system vulcanizations；N cyclohexyl 2 benzothiazole sulfenamide, N tert butyl benzothiazole 2 sulfenamide, N- oxygroup methylene -2-[4-morpholinodithio sulfenamide, N- ethoxy ethylene -2-[4-morpholinodithio sulfenamide, N, N'- diisopropyl - The sulfenamides such as 2-[4-morpholinodithio sulfenamide system vulcanization accelerator；Diphenylguanidine, di-o-tolyl guanidine, OTBG o tolylbiguanide etc. Guanidine system vulcanization accelerator.The use level of vulcanization accelerator relative to 100 mass parts of component of polymer be preferably 0.1 ~ 5 mass parts, More preferably 0.2 ~ 3 mass parts.
As silane coupling agent, it can be cited for example that vinyl trichlorosilane, vinyltriethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyl group front three Oxysilane, γ-methacryloxypropyl trimethoxy silane, N- (beta-aminoethyl)-gamma-amino propyl trimethoxy Silane, N- (beta-aminoethyl)-gamma-amino hydroxypropyl methyl dimethoxysilane, N- phenyl-gamma-amino propyl trimethoxy silicon It is alkane, γ-r-chloropropyl trimethoxyl silane, γ mercaptopropyitrimethoxy silane, γ aminopropyltriethoxy silane, double (3- (triethoxysilyl) propyl) disulphide, bis- (3- (triethoxysilyl) propyl) tetrasulfides, γ-three Trimethoxysilylpropyl dimethylthiocarbamoyl tetrasulfide, γ-trimethoxy-silylpropyl benzo thiophene Azoles tetrasulfide, 3- decoyl sulfenyl -1- propyl-triethoxysilicane and sulfydryl-thiocarboxylic acid ester oligomer.They can be used 1 Kind or more.As commercially available product, can be used the trade name " Si69 " of エ ボ ニ ッ Network corporation, " Si75 ", " Si266 " etc., The trade name " NXT Silane " of Momentive Performance Materials corporation, " NXT-Z30 ", " NXT- Z45 ", " NXT-Z60 ", " NXT-Z100 " etc..
The use level of silane coupling agent relative to 100 mass parts of supporting material be preferably 1 ~ 20 mass parts, more preferably 2 ~ 15 mass parts, further preferably 5 ~ 10 mass parts.
As extending oil, it can be cited for example that aromatic series mineral oil (viscosity-gravity constant (V.G.C. value) 0.900 ~ 1.049), cycloalkanes hydrocarbon system mineral oil (V.G.C. value 0.850 ~ 0.899) and paraffin mineral oil (V.G.C. value 0.790 ~ 0.849).The polycyclic aromatic content of extending oil is preferably shorter than 3 mass %, more preferably less than 1 mass %.The polycyclic aromatic content according to 346/92 method of institute of petroleum in britain is measured.In addition, the aromatic content (CA) of extending oil be preferably 20 mass % with On.These extending oils can be used a kind or more.
As the method for polymer composition involved in manufacture present embodiment, can be used each ingredient roller for example The method that mixing machine well known to grinding machine and Banbury mixer etc. is kneaded.
As compounding conditions, when cooperating the additive other than vulcanizing agent and vulcanization accelerator, melting temperature is usual It is 50 ~ 200 DEG C, preferably 80 ~ 190 DEG C, mixing time is usually 30 seconds ~ 30 minutes, preferably 1 minute ~ 30 minutes.Cooperate sulphur When agent, vulcanization accelerator, melting temperature is usually 100 DEG C or less, is preferably room temperature ~ 80 DEG C.In addition, be combined with vulcanizing agent, The composition of vulcanization accelerator usually carries out the vulcanizing treatments such as press cure and uses.As curing temperature, usually 120 ~ 200 DEG C, preferably 140 ~ 180 DEG C.
Polymer composition involved in present embodiment has excellent storage stability, and province's burnup is excellent, fits It shares in tire.
Embodiment
Hereinafter, present invention will be further described in detail through examples, but the present invention is not limited to these Examples.
Evaluation of physical property is carried out by following methods.
1. Mooney viscosity (ML1+4)
According to JIS K6300 (1994), the initial Mooney viscosity of polymer is measured at 100 DEG C.Then, in the perseverance of temperature 50 C Polymer, the Mooney viscosity after measurement 2 weeks (after promoting test) are placed in warm slot.
2. vinyl bonds resultant (unit: mol%)
By infrared spectrographic method, by the absorption peak 910cm of vinyl-1Neighbouring absorption intensity finds out the ethylene of polymer Base bonded amount.
3. being originated from the content (unit: quality %) of the monomeric unit of styrene
The content of the monomeric unit from styrene of polymer is found out by refractive index according to JIS K6383 (1995).
4. molecular weight distribution (Mw/Mn)
Under following condition (1) ~ (8), the equal molecule of weight average molecular weight (Mw) sum number is measured by gel permeation chromatography (GPC) method It measures (Mn), finds out the molecular weight distribution (Mw/Mn) of polymer.
(1) device: Dong ソ ー corporation HLC-8220
(2) splitter: Dong ソ ー corporation TSKgel SuperHM-H (2 series connection)
(3) measuring temperature: 40 DEG C
(4) carrier: tetrahydrofuran
(5) flow: 0.6mL/ minutes
(6) injection rate: 5 μ L
(7) detector: differential refractive index
(8) molecular weight standard: standard polystyren.
5. province's burnup
The short strip shape test film of width 1mm or 2mm, length 40mm are punched out from the sulfidization molding body of sheet, for test.It surveys Surely by determination of viscoelasticity device (Shang Dao manufacturing company system), the temperature of 70 DEG C of measurement under conditions of straining 1% and frequency 10Hz The loss angle tangent (tan δ (70 DEG C)) of test film under degree.When comparing province's burnup performance, if micro-structure is dramatically different, because The difference of motility and cause province's burnup performance dramatically different, therefore preferably compared one another in the close polymer of micro-structure Compared with.
[embodiment 1]
The production > of < modified conjugated diene polymer
(step 1)
It, will be in the polymer reactor by the cleaning of stainless steel polymer reactor and drying with agitating device of internal volume 20L The atmosphere in portion is replaced into drying nitrogen.Then, by industrial hexane (sumitomo chemical company system, trade name: hexane (general product), Density 0.68g/mL) 10.2kg, 1,3- butadiene 720g, styrene 80g, tetrahydrofuran 6.1mL and ethylene glycol Anaesthetie Ether 1.1mL is put into polymer reactor.Then, for the preparatory Non-toxic of impurity for making the inactivation to polymerization initiator play a role, It will contain after in the hexane solution investment polymer reactor of a small amount of n-BuLi (n-BuLi) as scavenger In the n-BuLi hexane solution investment polymer reactor of 13.42mmol, initiated polymerization.
Polymerization reaction carries out 3 hours.In polymerization reaction, the temperature in polymer reactor is adjusted to 65 DEG C, with 130rpm Mixing speed stirring polymer reactor in solution, it is continuous to supply 1,3-butadiene 1080g and benzene second into polymer reactor Alkene 120g.Then, polymer reactor temperature is remained 65 DEG C, while is stirred in polymer reactor with the mixing speed of 130rpm Gained polymeric solution is mixed, silicon tetrachloride 1.13mmol is added into polymeric solution, is stirred 15 minutes.
(step 2)
After step 1, polymer reactor temperature is remained 65 DEG C, while stirring in polymer reactor with the mixing speed of 130rpm Gained polymeric solution is mixed, [3- (diethylamino) propyl] trimethoxy silane of addition as modifying agent into polymeric solution 8.90mmol is stirred 15 minutes.
(step 3)
After step 2, polymer reactor temperature is remained 65 DEG C, while stirring in polymer reactor with the mixing speed of 130rpm Gained polymeric solution is mixed, adds the hexane solution of the n-BuLi containing 8.90mmol thereto, is stirred 15 minutes.Then, will In hexane solution 5mL investment polymer reactor comprising methanol 0.8mL, polymer solution is stirred 5 minutes.
By acrylic acid 2- tert-butyl -6- (3- tert-butyl -2- hydroxy-5-methyl base benzyl) -4- methylbenzene base ester (Sumitomo Learn corporation, trade name: ス ミ ラ イ ザ ー GM) (Sumitomo Chemical is public for 8.0g and pentaerythrite four (3- laurel thiohydracrylic acid ester) Department system, trade name: ス ミ ラ イ ザ ー TP-D) 4.0g investment polymer reactor in, then, make being volatilized into polymer solution Major part in point was evaporated at normal temperature with 24 hours, was further dried under reduced pressure at 55 DEG C 12 hours, and modified conjugation two is obtained Alkene based polymer 1.
The preparation > of < polymer composition
By the modified conjugated diene polymer 1 of 100 mass parts, silica (デ グ ッ サ corporation, the quotient of 80.0 mass parts The name of an article: ウ Le ト ラ シ Le VN3-G), the silane coupling agent (デ グ ッ サ corporation, trade name: Si69) of 6.4 mass parts, 5.0 matter Measure the carbon black (Mitsubishi Chemical Ind's system, trade name: ダ イ ヤ Block ラ ッ Network N339) of part, extending oil (the ジ ャ パ of 40.0 mass parts Application エ ナ ジ ー corporation, trade name: JOMO プ ロ セ ス NC-140), the anti-aging agents of 2.0 mass parts (sumitomo chemical company system, Trade name: ア Application チ ゲ Application 6C), the wax (the emerging chemical industrial company's system of imperial palace, trade name: サ Application ノ ッ Network N) of 1.5 mass parts, The wax (ス ト ラ ク ト ー Le corporation, trade name: EF44) of 1 mass parts, the stearic acid of 2.0 mass parts, 2.0 mass parts zinc white It is kneaded with Labo Plastomill, prepares polymer composition.
The production > of < vulcanized tablet
Into resultant polymer composition, add vulcanization accelerator (sumitomo chemical company system, trade name: ソ Network シ ノ ー Le CZ) 1.5 mass parts, vulcanization accelerator (sumitomo chemical company system, trade name: ソ Network シ ノ ー Le D) 2.0 mass parts, 1.5 mass of sulphur Part, it is shaped to piece with 6 inch rollers, which is heated to 55 minutes at 160 DEG C to vulcanize, makes vulcanized tablet.
[embodiment 2]
In step 3, the hexane solution of the n-BuLi containing 8.90mmol is being changed to the n-BuLi containing 17.80mmol just In addition to this hexane solution in the same manner as example 1, obtains modified conjugated diene polymer 2.In addition, using should In addition to this polymer in the same manner as example 1, prepares polymer composition, makes vulcanized tablet.
[comparative example 1]
In step 3, it is not added with the hexane solution containing n-BuLi, in addition to this, in the same manner as example 1, is obtained Modified conjugated diene polymer C1.In addition, using the polymer, in addition to this, in the same manner as example 1, preparation Polymer composition makes vulcanized tablet.
The vinyl bonds resultant of modified conjugated diene polymer obtained in embodiment 1,2 and comparative example 1, styrene list The content of member, n-BuLi used in step 3 are relative to the molar ratio of modifying agent used in step 2, Mooney viscosity and vulcanization Province's burnup of piece evaluation result is shown in table 1.Here, initially and promoting the difference after test smaller in Mooney viscosity in table 1 Then storage stability is more excellent, and saving burnup is the relative value that 100 are denoted as with comparative example 1, and numerical value Yue great Ze saves burnup and gets over It is excellent.
[table 1]
。
[embodiment 3]
The production > of < modified conjugated diene polymer
(step 1)
It, will be in the polymer reactor by the cleaning of stainless steel polymer reactor and drying with agitating device of internal volume 20L The atmosphere in portion is replaced into drying nitrogen.Then, by " hexane (general product) " 10.2kg, 1,3-butadiene 608g, styrene 192g, In tetrahydrofuran 6.1mL and ethylene glycol Anaesthetie Ether 4.6mL investment polymer reactor.Then, by the hexane of a small amount of n-BuLi After solution is put into polymer reactor, by the n-BuLi hexane solution investment polymer reactor containing 15.20mmol, cause Polymerization reaction.
Polymerization reaction carries out 3 hours.In polymerization reaction, the temperature in polymer reactor is adjusted to 65 DEG C, with 130rpm Mixing speed stirring polymer reactor in solution, it is continuous to supply 1,3-butadiene 912g and benzene second into polymer reactor Alkene 288g.Then, polymer reactor temperature is remained 65 DEG C, while is stirred in polymer reactor with the mixing speed of 130rpm Gained polymeric solution is mixed, silicon tetrachloride 1.16mmol is added into polymeric solution, is stirred 15 minutes.
(step 2)
After step 1, polymer reactor temperature is remained 65 DEG C, while stirring in polymer reactor with the mixing speed of 130rpm Gained polymeric solution is mixed, [3- (diethylamino) propyl] trimethoxy silane 10.55mmol, stirring are added into polymeric solution 15 minutes.
(step 3)
After step 2, polymer reactor temperature is remained 65 DEG C, while stirring in polymer reactor with the mixing speed of 130rpm Gained polymeric solution is mixed, adds the hexane solution of the n-BuLi containing 10.55mmol thereto, is stirred 15 minutes.Then, will In hexane solution 5mL investment polymer reactor comprising methanol 0.8mL, polymer solution is stirred 5 minutes.
By in " ス ミ ラ イ ザ ー GM " 8.0g and " ス ミ ラ イ ザ ー TP-D " 4.0g investment polymer reactor, then, make Major part in volatile ingredient in polymer solution was evaporated at normal temperature with 24 hours, was further dried under reduced pressure 12 at 55 DEG C Hour, obtain modified conjugated diene polymer 3.
The preparation of < polymer composition and the production > of vulcanized tablet
Using modified conjugated diene polymer 3, in addition to this, in the same manner as example 1, combination of polymers is prepared Object makes vulcanized tablet.
[embodiment 4]
In step 3, the hexane solution of the n-BuLi containing 10.55mmol is changed to the n-BuLi's containing 15.83mmol In addition to this hexane solution in mode same as Example 3, obtains modified conjugated diene polymer 4.In addition, using In addition to this polymer in mode same as Example 3, prepares polymer composition, makes vulcanized tablet.
[embodiment 5]
In step 3, the n-BuLi hexane solution containing 21.10mmol is added, in addition to this, with side same as Example 3 Formula obtains modified conjugated diene polymer 5.In addition, using the polymer, in addition to this, with side same as Example 3 Formula prepares polymer composition, makes vulcanized tablet.
[comparative example 2]
In step 3, it is not added with the hexane solution containing n-BuLi, in addition to this, in mode same as Example 3, is obtained Modified conjugated diene copolymer C2.In addition, using the polymer, in addition to this, with mode same as Example 3, preparation Polymer composition makes vulcanized tablet.
The vinyl bonds resultant of modified conjugated diene polymer obtained in embodiment 3 ~ 5 and comparative example 2, styrene list The content of member, n-BuLi used in step 3 are relative to the molar ratio of modifying agent used in step 2, Mooney viscosity and vulcanization Province's burnup of piece evaluation result is shown in table 2.Here, province's burnup in table 2 is the relative value for being denoted as 100 with comparative example 2.
[table 2]
。
[embodiment 6]
The production > of < modified conjugated diene polymer
(step 1')
It, will be in the polymer reactor by the cleaning of stainless steel polymer reactor and drying with agitating device of internal volume 20L The atmosphere in portion is replaced into drying nitrogen.Then, by " hexane (general product) " 10.2kg, 1,3-butadiene 608g, styrene 192g, Tetrahydrofuran 6.1mL, ethylene glycol Anaesthetie Ether 4.6mL and bis- (diethylamino) ethylene methacrylic base silane 3.66mmol investment are poly- It closes in reactor.Then, after the hexane solution of a small amount of n-BuLi being put into polymer reactor, it will contain 11.70mmol's N-BuLi hexane solution is put into polymer reactor, initiated polymerization.
After carrying out 0.5 hour polymerization reaction, will be bis- (diethylamino) ethylene methacrylic base silane 4.88mmol investment polymerization In reactor, 2.5 hours polymerization reactions of further progress.It amounts in 3 hours polymerization reactions, by the temperature in polymer reactor 65 DEG C are adjusted to, continuously supplies 1 into polymer reactor with the solution in the mixing speed stirring polymer reactor of 130rpm, 3- butadiene 912g and styrene 288g.
(step 3')
After step 1', polymer reactor temperature is remained 65 DEG C, while with the mixing speed of 130rpm in polymer reactor Stirring gained polymeric solution, adds the hexane solution of the n-BuLi containing 17.08mmol thereto, stirs 15 minutes.Then, By in the hexane solution 5mL investment polymer reactor comprising methanol 0.8mL, polymer solution is stirred 5 minutes.
By in " ス ミ ラ イ ザ ー GM " 8.0g and " ス ミ ラ イ ザ ー TP-D " 4.0g investment polymer reactor, then, make Major part in volatile ingredient in polymer solution was evaporated at normal temperature with 24 hours, was further dried under reduced pressure 12 at 55 DEG C Hour, obtain modified conjugated diene polymer 6.
The preparation of < polymer composition and the production > of vulcanized tablet
Using modified conjugated diene polymer 6, in addition to this, in the same manner as example 1, combination of polymers is prepared Object makes vulcanized tablet.
[embodiment 7]
In step 3', the hexane solution of the n-BuLi containing 17.08mmol is changed to the n-BuLi's containing 34.16mmol In addition to this hexane solution in the same manner as in example 6, obtains modified conjugated diene polymer 7.In addition, using In addition to this polymer in the same manner as in example 6, prepares polymer composition, makes vulcanized tablet.
[comparative example 3]
In step 3', it is not added with the hexane solution containing n-BuLi, in addition to this, in the same manner as in example 6, is obtained Modified conjugated diene polymer C3.In addition, using the polymer, in addition to this, in the same manner as in example 6, preparation Polymer composition makes vulcanized tablet.
The vinyl bonds resultant of modified conjugated diene polymer obtained in embodiment 6,7 and comparative example 3, styrene list The content of member, n-BuLi used in step 3' are relative to the molar ratio of modifying agent used in step 1', Mooney viscosity and sulphur Change piece province's burnup evaluation result is shown in table 3.Here, province's burnup in table 3 is be denoted as 100 with comparative example 3 opposite Value.
[table 3]
。
[embodiment 8]
The production > of < modified conjugated diene polymer
(step 1')
Step 1' is carried out in the same manner as in example 6.
(step 2')
Step 1 ' after, polymer reactor temperature is remained 65 DEG C, while with the mixing speed of 130rpm in polymer reactor Stirring gained polymeric solution, N- (3- dimethylaminopropyl) acrylamide 11.70mmol, stirring 15 are added into polymeric solution Minute.
(step 3')
After step 2', polymer reactor temperature is remained 65 DEG C, while with the mixing speed of 130rpm in polymer reactor Stirring gained polymeric solution, adds the hexane solution of the n-BuLi containing 17.08mmol thereto, stirs 15 minutes.Then, By in the hexane solution 5mL investment polymer reactor comprising methanol 0.8mL, polymer solution is stirred 5 minutes.
By in " ス ミ ラ イ ザ ー GM " 8.0g and " ス ミ ラ イ ザ ー TP-D " 4.0g investment polymer reactor, then, make Major part in volatile ingredient in polymer solution was evaporated at normal temperature with 24 hours, was further dried under reduced pressure 12 at 55 DEG C Hour, obtain modified conjugated diene polymer 8.
The preparation of < polymer composition and the production > of vulcanized tablet
Using modified conjugated diene polymer 8, in addition to this, in the same manner as example 1, combination of polymers is prepared Object makes vulcanized tablet.
[embodiment 9]
In step 3', the hexane solution of the n-BuLi containing 17.08mmol is changed to the n-BuLi's containing 40.48mmol In addition to this hexane solution in mode same as Example 8, obtains modified conjugated diene polymer 9.In addition, using In addition to this polymer in mode same as Example 8, prepares polymer composition, makes vulcanized tablet.
[comparative example 4]
In step 3', it is not added with the hexane solution containing n-BuLi, in addition to this, in mode same as Example 8, is obtained Modified conjugated diene copolymer C4.In addition, using the polymer, in addition to this, with mode same as Example 8, preparation Polymer composition makes vulcanized tablet.
The vinyl bonds resultant of modified conjugated diene polymer obtained in embodiment 8,9 and comparative example 4, styrene list The content of member, n-BuLi used in step 3' are relative to the molar ratio of modifying agent used in step 1', Mooney viscosity and sulphur Change piece province's burnup evaluation result is shown in table 4.Here, province's burnup in table 4 is be denoted as 100 with comparative example 4 opposite Value.
[table 4]
。
[embodiment 10]
The production > of < modified conjugated diene polymer
(step 1)
It, will be in the polymer reactor by the cleaning of stainless steel polymer reactor and drying with agitating device of internal volume 20L The atmosphere in portion is replaced into drying nitrogen.Then, by " hexane (general product) " 10.2kg, 1,3-butadiene 608g, styrene 192g, In tetrahydrofuran 6.1mL and ethylene glycol Anaesthetie Ether 4.6mL investment polymer reactor.Then, by the hexane of a small amount of n-BuLi After solution is put into polymer reactor, by the n-BuLi hexane solution investment polymer reactor containing 15.20mmol, cause Polymerization reaction.
Polymerization reaction carries out 3 hours.In polymerization reaction, the temperature in polymer reactor is adjusted to 65 DEG C, with 130rpm Mixing speed stirring polymer reactor in solution, it is continuous to supply 1,3-butadiene 912g and benzene second into polymer reactor Alkene 288g.Then, polymer reactor temperature is remained 65 DEG C, while is stirred in polymer reactor with the mixing speed of 130rpm Gained polymeric solution is mixed, silicon tetrachloride 1.16mmol is added into polymeric solution, is stirred 15 minutes.
(step 2)
After step 1, polymer reactor temperature is remained 65 DEG C, while stirring in polymer reactor with the mixing speed of 130rpm Gained polymeric solution is mixed, [3- (diethylamino) propyl] trimethoxy silane 10.55mmol, stirring are added into polymeric solution 15 minutes.
(step 3)
After step 2, polymer reactor temperature is remained 65 DEG C, while stirring in polymer reactor with the mixing speed of 130rpm Gained polymeric solution is mixed, adds the hexane solution of the n-BuLi containing 15.83mmol thereto, is stirred 15 minutes.Then, will In hexane solution 5mL investment polymer reactor comprising methanol 0.8mL, polymer solution is stirred 5 minutes.
By in " ス ミ ラ イ ザ ー GM " 8.0g and " ス ミ ラ イ ザ ー TP-D " 4.0g investment polymer reactor, it is polymerize Object solution.It evaporates a part in the polymer solution with 24 hours at normal temperature, is further dried under reduced pressure 12 at 55 DEG C Hour, ML viscosity at this time is 41.Then, after by the polymer solution by stripping desolventizing, with 70 DEG C of heated-air drying Machine is 24 hours dry, obtains modified conjugated diene polymer 10.The ML viscosity of modified conjugated diene polymer 10 is 44.
The preparation of < polymer composition and the production > of vulcanized tablet
Using modified conjugated diene polymer 10, in addition to this, in the same manner as example 1, combination of polymers is prepared Object makes vulcanized tablet.
[comparative example 5]
In step 3, it is not added with the hexane solution containing n-BuLi, in addition to this, in mode same as in Example 10, is obtained Polymer solution.It evaporates a part in the polymer solution with 24 hours at normal temperature, is further depressurized at 55 DEG C dry Dry 12 hours, ML viscosity at this time was 46.Then, by the polymer solution with mode desolventizing same as in Example 10, dry It is dry, obtain modified conjugated diene polymer C5.The ML viscosity of modified conjugated diene polymer C5 is 63.In addition, using should In addition to this polymer in mode same as in Example 10, prepares polymer composition, makes vulcanized tablet.
The vinyl bonds resultant of modified conjugated diene polymer obtained in embodiment 10 and comparative example 5, styrene list The content of member, n-BuLi used in step 3 are relative to the molar ratio of modifying agent used in step 2, Mooney viscosity and vulcanization Province's burnup of piece evaluation result is shown in table 5.Here, province's burnup in table 5 is the relative value for being denoted as 100 with comparative example 5. In addition, the difference using the value after the value and stripping and heated-air drying being dried under reduced pressure is smaller, then storage stability is got in Mooney viscosity It is excellent.
[table 5]
。

Claims (7)

1. the manufacturing method of modified conjugated diene polymer, including makes conjugated diene polymer and Organometallic compounds The step of object is had an effect, the conjugated diene polymer have unit based on the monomer comprising conjugated diene compound, With the unit based on the modifying agent with silicon atom, tin atom, germanium atom or phosphorus atoms.
2. according to the method described in claim 1, wherein, the conjugated diene polymer has in end is based on the modification The unit of agent.
3. method according to claim 1 or 2, wherein the conjugated diene polymer has in strand to be based on The unit of the modifying agent.
4. method described according to claim 1 ~ any one of 3, wherein the modifying agent includes to have to tie shown in formula (5) The compound of structure,
[changing 1]
In formula, R1Indicate alkyl, alkenyl, cycloalkenyl or aryl, M1Indicate silicon atom, tin atom, germanium atom or phosphorus atoms, L1Table Show halogen atom or oxyl, R1And L1There are it is multiple when, respectively can be identical or different, M1It is former for silicon atom, tin atom or germanium The period of the day from 11 p.m. to 1 a.m, n indicate that 0, m and l each independently represents 0 ~ 4 integer for meeting m+l=4, M1When for phosphorus atoms, n is 0 or 1, m and l Each independently represent 0 ~ 3 integer for meeting m+l=3.
5. method described according to claim 1 ~ any one of 4, wherein the modifying agent includes to have to tie shown in formula (6) The compound of structure,
[changing 2]
In formula, X1、X2And X3It each independently represents alkyl, oxyl, halogen atom or can gather with the conjugated diene Close the functional group of the reactive terminal reaction of object, R61And R62Each independently represent hydrogen atom or alkyl, R61And R62There are multiple When, it respectively can be identical or different, A1Indicate have in oxygen atom, nitrogen-atoms, phosphorus atoms, sulphur atom and silicon atom extremely A kind of organic group of few atom, optionally has ring structure, X1、X2Or X3Structure in a part optionally and A1In one Divide bonding, a indicates 0 ~ 10 integer.
6. method described according to claim 1 ~ any one of 5, wherein the modifying agent includes to have to tie shown in formula (7) The compound of structure,
[changing 3]
In formula, R71Indicate that hydrogen atom or alkyl, s indicate 0 or 1, R72Indicate alkylene, X7、X8And X9Each independently represent substitution Amino or optionally with substituent group alkyl, X7、X8And X9In at least one be replace amino.
7. including the invention further relates to the manufacturing method of polymer composition to by described in any one of claim 1 ~ 6 Method production 100 mass parts of modified conjugated diene copolymer be kneaded 10 ~ 150 mass parts supporting material the step of.
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